KR20210023952A - Compounds comprising benzophenone group, Organic electronic device comprising organic layers comprising the photo-cured of the monomer compounds - Google Patents

Compounds comprising benzophenone group, Organic electronic device comprising organic layers comprising the photo-cured of the monomer compounds Download PDF

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KR20210023952A
KR20210023952A KR1020210025089A KR20210025089A KR20210023952A KR 20210023952 A KR20210023952 A KR 20210023952A KR 1020210025089 A KR1020210025089 A KR 1020210025089A KR 20210025089 A KR20210025089 A KR 20210025089A KR 20210023952 A KR20210023952 A KR 20210023952A
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이성구
서민혜
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한국생산기술연구원
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
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    • C07F9/50—Organo-phosphines
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • H10K50/14—Carrier transporting layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene

Abstract

The present invention relates to a compound comprising a benzophenone functional group represented by chemical formula I, Ar-(R_1-R_2-B_p)_m or chemical formula II and to an organic electronic device comprising an organic layer including a photocured material of the compound, wherein the benzophenone functional group has a photo-crosslinking function.

Description

벤조페논 작용기 함유 화합물, 상기 화합물의 광경화물을 포함한 유기물층을 구비한 유기전자소자 {Compounds comprising benzophenone group, Organic electronic device comprising organic layers comprising the photo-cured of the monomer compounds}[Compounds comprising benzophenone group, Organic electronic device comprising organic layers comprising the photo-cured of the monomer compounds}

본 발명은 벤조페논 작용기 함유 화합물, 상기 화합물의 광경화물을 포함한 유기물층을 구비한 유기전자소자에 관한 것이다.The present invention relates to an organic electronic device including a benzophenone functional group-containing compound and an organic material layer including a photocured product of the compound.

일반적으로, 액정표시장치(LCD), 유기 EL 디스플레이 등의 ITO 전극 형성용을 위한 레지스트 재료나 층간 절연막, 회로 보호막, 액정 디스플레이의 컬러 필터 제조용 착색 안료 분산 레지스트, 유기 EL 디스플레이용 격벽재 등의 영구 막형성 재료로서 광경화성 수지 조성물이 폭넓게 사용되고 있다. 이러한 수지 조성물은 종래 증착 방식으로 유기발광소자(Organic Light-Emitting Diode, OLED)에 적용되었으나, 이러한 증착 방식에 의해서는 대형 디스플레이의 제작에 어려움이 있고 고가의 장비가 사용되는 문제점이 있다. In general, a resist material for forming ITO electrodes such as a liquid crystal display (LCD), an organic EL display, an interlayer insulating film, a circuit protective film, a colored pigment dispersion resist for manufacturing a color filter for a liquid crystal display, a barrier material for an organic EL display, etc. are permanently used. Photocurable resin compositions are widely used as film-forming materials. Such a resin composition has been applied to an organic light-emitting device (OLED) by a conventional deposition method, but there is a problem in that it is difficult to manufacture a large display and expensive equipment is used by this deposition method.

이에, 최근에는 대형 디스플레이의 제작을 위해 잉크젯과 같은 용액공정을 사용하는 방안이 대두되고 있다. 그러나. 용액 공정을 이용한 OLED 디스플레이의 경우에는 다층 박막의 형성이 어렵고, 이로 인하여 소자의 효율이 낮은 문제점이 있다. Accordingly, in recent years, a method of using a solution process such as an ink jet has emerged for manufacturing a large display. But. In the case of an OLED display using a solution process, it is difficult to form a multilayer thin film, and thus, there is a problem in that the efficiency of the device is low.

이러한 문제점을 해결하기 위하여, 에폭시, 아크릴레이트 등 경화가 가능한 작용기를 가진 물질을 합성하여 유기발광소자의 소재로 사용하고자 하는 연구가 진행되고 있으나, 이러한 작용기를 가진 물질은 경화에 고온을 요구하거나 또는 경화과정에서 부산물(byproduct)을 형성하는 문제점을 갖고 있다.In order to solve this problem, research is being conducted to synthesize a material having a curable functional group such as epoxy and acrylate and use it as a material for an organic light emitting device. However, a material having such a functional group requires a high temperature for curing or It has a problem of forming a byproduct during the curing process.

본 발명은 상술한 문제점을 해결하기 위하여 이루어진 것으로, 상온에서 광경화에 의해 고분자 필름을 형성할 수 있는 화합물 및 상기 화합물의 광경화물을 포함한 유기층을 제공하는 것을 일 목적으로 한다.The present invention has been made to solve the above-described problems, and an object thereof is to provide a compound capable of forming a polymer film by photocuring at room temperature and an organic layer including a photocured product of the compound.

또한, 본 발명은 광가교가 가능한 기능을 가진 벤조페논기를 구비한 화합물을 신규 합성하여 코팅에 의해 소자를 제작함으로써 다층 박막 및 패턴을 형성하는 것을 다른 목적으로 한다.In addition, another object of the present invention is to form a multi-layered thin film and pattern by newly synthesizing a compound having a benzophenone group having a function capable of photo-crosslinking and fabricating a device by coating.

또한, 본 발명은 광개시제와 같은 물질이 불순물로 잔류하여 소자 성능을 저하시키는 것을 방지시키는 것을 또 다른 목적으로 한다.In addition, another object of the present invention is to prevent a material such as a photoinitiator from remaining as an impurity and deteriorating device performance.

본 발명은 또한 상기 유기물층을 포함하는 유기전자소자를 제공하는 것을 또 다른 목적으로 한다.Another object of the present invention is to provide an organic electronic device including the organic material layer.

본 발명의 제1 양태에 따르면, 하기 화학식 I 또는 화학식 II로 표시되는 벤조페논 작용기 함유 화합물이 제공된다:According to a first aspect of the present invention, there is provided a compound containing a benzophenone functional group represented by the following formula (I) or formula (II):

[화학식 I][Formula I]

Ar-(R1-R2-Bp)m Ar-(R 1 -R 2 -Bp) m

상기 화학식에서, In the above formula,

m은 1 내지 10 이고, m is 1 to 10,

Ar은 m차 연결기를 갖는 치환 또는 비치환된 C6-C60 아릴기, m차 연결기를 갖는 치환 또는 비치환된 C3-C60 헤테로아릴기 또는 m차 연결기를 갖는 치환 또는 비치환된 융합된 C6-C60 아릴기이고, Ar is a substituted or unsubstituted C 6 -C 60 aryl group having an m-th linking group, a substituted or unsubstituted C 3 -C 60 heteroaryl group having an m-th linking group, or a substituted or unsubstituted fusion having an m-th linking group Is a C 6 -C 60 aryl group,

R1 및 R2는 각각 독립적으로, 단순 결합, -O-, 치환 또는 비치환된 C6-C30아릴렌기, 치환 또는 비치환된 C3-C30 헤테로아릴렌기, 치환 또는 비치환된 C1-C10 알킬렌기이고, R 1 and R 2 are each independently a simple bond, -O-, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 1 -C 10 alkylene group,

Bp은 벤조페논 작용기로부터 유래된 1가 연결기이다.Bp is a monovalent linking group derived from a benzophenone functional group.

[화학식 II][Formula II]

Figure pat00001
Figure pat00001

상기 화학식에서, In the above formula,

n은 1 이상이고, n is 1 or more,

Ar'은 m차 연결기를 갖는 치환 또는 비치환된 C6-C60 아릴기, m차 연결기를 갖는 치환 또는 비치환된 C3-C60 헤테로아릴기 또는 m차 연결기를 갖는 치환 또는 비치환된 융합된 C6-C60 아릴기이고, Ar' is a substituted or unsubstituted C 6 -C 60 aryl group having an m-th linking group, a substituted or unsubstituted C 3 -C 60 heteroaryl group having an m-th linking group, or a substituted or unsubstituted having an m-th linking group A fused C 6 -C 60 aryl group,

R3 및 R4는 각각 독립적으로, 단순 결합, -O-, 치환 또는 비치환된 C6-C30아릴렌기, 치환 또는 비치환된 C3-C30 헤테로아릴렌기, 치환 또는 비치환된 C6-C30 융합된 아릴렌기, 치환 또는 비치환된 C1-C10 알킬렌기이고, R 3 and R 4 are each independently a simple bond, -O-, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 6 -C 30 fused arylene group, substituted or unsubstituted C 1 -C 10 alkylene group,

Bp'은 벤조페논 작용기로부터 유래된 1가 연결기이다.Bp' is a monovalent linking group derived from a benzophenone functional group.

본원 명세서에서 헤테로원자는 비제한적으로, N, O, Si를 들 수 있으나, 이에 제한되는 것은 아니다.In the present specification, the heteroatom includes, but is not limited to, N, O, and Si, but is not limited thereto.

본 발명의 제2 양태에 따르면, 상기 제1 양태에서 상기 벤조페논 작용기를 포함하는 화합물이 하기 화학식 1 내지 11로부터 선택된 1종 또는 2종 이상의 화합물인 벤조페논 작용기 함유 화합물이 제공된다:According to a second aspect of the present invention, there is provided a benzophenone functional group-containing compound in which the compound containing the benzophenone functional group in the first aspect is one or two or more compounds selected from the following Formulas 1 to 11:

[화학식 1][Formula 1]

Figure pat00002
Figure pat00002

[화학식 2][Formula 2]

Figure pat00003
Figure pat00003

[화학식 3][Formula 3]

Figure pat00004
Figure pat00004

[화학식 4][Formula 4]

Figure pat00005
Figure pat00005

[화학식 5][Formula 5]

Figure pat00006
Figure pat00006

[화학식 6][Formula 6]

Figure pat00007
Figure pat00007

(상기에서 n은 1 이상, 바람직하게는 1 내지 4이다)(In the above, n is 1 or more, preferably 1 to 4)

[화학식 7][Formula 7]

Figure pat00008
Figure pat00008

[화학식 8][Formula 8]

Figure pat00009
Figure pat00009

[화학식 9][Formula 9]

Figure pat00010
Figure pat00010

[화학식 10][Formula 10]

Figure pat00011
Figure pat00011

[화학식 11][Formula 11]

Figure pat00012
.
Figure pat00012
.

본 발명의 제3 양태에 따르면, 상기 제1 양태 또는 제2 양태에서 상기 Ar 또는 Ar'이 하기 화합물중 하나인 것을 특징으로 하는 페논 작용기 함유 화합물이 제공된다:According to a third aspect of the present invention, there is provided a phenone functional group-containing compound, characterized in that Ar or Ar' is one of the following compounds in the first or second aspect:

Figure pat00013
Figure pat00013
Figure pat00014
Figure pat00014
Figure pat00015
Figure pat00015
Figure pat00016
Figure pat00016
Figure pat00017
Figure pat00017
Figure pat00018
Figure pat00018
Figure pat00019
Figure pat00019
Figure pat00020
Figure pat00020
Figure pat00021
Figure pat00021
Figure pat00022
Figure pat00022
Figure pat00023
Figure pat00023

본 발명의 제4 양태에 따르면, 상기 제1 양태 내지 제3 양태중 어느 하나의 양태의 벤조페논 작용기 함유 화합물을 포함하는 광경화 조성물이 제공된다.According to a fourth aspect of the present invention, there is provided a photocurable composition comprising the benzophenone functional group-containing compound of any one of the first to third aspects.

본 발명의 제5 양태에 따르면, 제1전극; 제2전극; 및 상기 제1전극과 상기 제2전극 사이에 상기 제1 양태 내지 제3 양태중 어느 하나의 양태의 벤조페논 작용기 함유 화합물의 광경화물을 포함한 유기물층을 구비한 유기전자소자가 제공된다.According to a fifth aspect of the present invention, there is provided a first electrode; A second electrode; And an organic material layer including a photocured product of the benzophenone functional group-containing compound of any one of the first to third aspects between the first electrode and the second electrode.

본 발명의 제6 양태에 따르면, 상기 제5 양태에서 상기 유기물층이 정공수송층이고, 상기 정공수송층이 하기 화학식 1 내지 6의 화합물 중 1종 이상의 벤조페논 작용기 함유 화합물의 광경화물을 포함하는 유기전자소자가 제공된다:According to a sixth aspect of the present invention, in the fifth aspect, the organic material layer is a hole transport layer, and the hole transport layer is an organic electronic device comprising a photocured product of at least one benzophenone functional group-containing compound among the compounds represented by the following formulas 1 to 6 Is provided:

[화학식 1][Formula 1]

Figure pat00024
Figure pat00024

[화학식 2][Formula 2]

Figure pat00025
Figure pat00025

[화학식 3][Formula 3]

Figure pat00026
Figure pat00026

[화학식 4][Formula 4]

Figure pat00027
Figure pat00027

[화학식 5][Formula 5]

Figure pat00028
Figure pat00028

[화학식 6][Formula 6]

Figure pat00029
Figure pat00029

(상기에서 n은 1 이상, 바람직하게는 1 내지 4이다)(In the above, n is 1 or more, preferably 1 to 4)

본 발명의 제7 양태에 따르면, 상기 유기물층이 전자수송층이고, 상기 전자수송층이 하기 화학식 7 내지 11의 화합물 중 1종 이상의 광경화물을 포함하는 유기전자소자가 제공된다:According to a seventh aspect of the present invention, there is provided an organic electronic device in which the organic material layer is an electron transport layer, and the electron transport layer includes at least one photocured product of the compounds represented by the following Formulas 7 to 11:

[화학식 7][Formula 7]

Figure pat00030
Figure pat00030

[화학식 8][Formula 8]

Figure pat00031
Figure pat00031

[화학식 9][Formula 9]

Figure pat00032
Figure pat00032

[화학식 10][Formula 10]

Figure pat00033
Figure pat00033

[화학식 11][Formula 11]

Figure pat00034
Figure pat00034

본 발명의 제8 양태에 따르면, 제 1 기판과; 상기 제 1 기판에 위치하는 구동 박막트랜지스터와; 상기 제 1 기판에 위치하며 상기 구동 박막트랜지스터에 연결되는 발광다이오드로서, 제1 양태 내지 제 양태 중 어느 하나의 양태의 벤조페논 작용기 함유 화합물의 광경화물을 적어도 하나의 유기물층에 포함하는 유기전자소자와; 상기 유기전자소자를 덮고 상기 제 1 기판과 합착되는 제 2 기판을 포함하는 표시 장치가 제공된다.According to an eighth aspect of the present invention, there is provided a first substrate; A driving thin film transistor positioned on the first substrate; An organic electronic device comprising a photocured product of a benzophenone functional group-containing compound according to any one of the first to the first embodiments in at least one organic material layer as a light emitting diode positioned on the first substrate and connected to the driving thin film transistor, and ; A display device is provided that covers the organic electronic device and includes a second substrate bonded to the first substrate.

광경화형의 장점은 경화가 일어남으로써 다층 박막을 형성할 수 있을 뿐 아니라 패터닝이 가능하다는 것이다. The advantage of the photo-curing type is that it is possible to form a multilayer thin film as well as patterning by curing.

본 발명에 따르면, 벤조페논 작용기를 포함하는 OLED 물질을 제조하고, UV에 의한 벤조페논 작용기의 CO 기와 이웃한 물질의 수소 간의 가교결합을 이용하여 다층 박막의 형성이 가능하게 된다. 즉, 다층 박막 및 패턴 형성을 위해 벤조페논 작용기를 갖는 물질을 합성하고 조사에 의해 단단한 박막이 형성된다. 또한, 형성된 박막은 용매에 의해 에칭됨으로써 패턴이 형성된 유기박막으로 형성될 수 있고, 이를 이용한 유기전자소자의 제작이 가능하게 된다.According to the present invention, an OLED material containing a benzophenone functional group is prepared, and a multilayer thin film can be formed by using a crosslinking between the CO group of the benzophenone functional group and hydrogen of an adjacent material by UV. That is, a material having a benzophenone functional group is synthesized to form a multilayer thin film and a pattern, and a hard thin film is formed by irradiation. In addition, the formed thin film may be formed as an organic thin film on which a pattern is formed by being etched by a solvent, and an organic electronic device may be manufactured using the same.

본 발명에 따라 용액공정으로 제작된 유기전자소자는 OLED 유기층 형성을 위한 조성물에 별도의 광개시제가 사용되지 않으므로 미반응된 광개시제 불순물에 의한 OLED 소자의 성능 저하의 문제가 발생될 수 있고, 또한, 기존 증착공정에 의해 제작된 소자 대비 동등 이상의 성능을 가질 수 있다. In the organic electronic device manufactured by the solution process according to the present invention, since a separate photoinitiator is not used in the composition for forming the OLED organic layer, the problem of deterioration of the performance of the OLED device due to unreacted photoinitiator impurities may occur. It can have a performance equal to or higher than that of a device manufactured by a deposition process.

본 명세서에서 사용된 모든 기술적 및 과학적 용어들은, 달리 정의되지 않는 한, 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.All technical and scientific terms used herein have the same meaning as commonly understood by an expert skilled in the art, unless otherwise defined. In general, the nomenclature used in this specification is well known and commonly used in the art.

본 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout this specification, when a certain part "includes" a certain constituent element, it means that other constituent elements may be further included rather than excluding other constituent elements unless otherwise stated.

이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명에 따르면, 하기 화학식 I 또는 화학식 II로 표시되는 벤조페논 작용기 함유 화합물이 제공된다:According to the present invention, there is provided a compound containing a benzophenone functional group represented by the following formula (I) or formula (II):

[화학식 I][Formula I]

Ar-(R1-R2-Bp)m Ar-(R 1 -R 2 -Bp) m

상기 화학식에서, In the above formula,

m은 1 내지 10 이고, m is 1 to 10,

Ar은 m차 연결기를 갖는 치환 또는 비치환된 C6-C60 아릴기, m차 연결기를 갖는 치환 또는 비치환된 C3-C60 헤테로아릴기 또는 m차 연결기를 갖는 치환 또는 비치환된 융합된 C6-C60 아릴기이고, Ar is a substituted or unsubstituted C 6 -C 60 aryl group having an m-th linking group, a substituted or unsubstituted C 3 -C 60 heteroaryl group having an m-th linking group, or a substituted or unsubstituted fusion having an m-th linking group Is a C 6 -C 60 aryl group,

R1 및 R2는 각각 독립적으로, 단순 결합, -O-, 치환 또는 비치환된 C6-C30아릴렌기, 치환 또는 비치환된 C3-C30 헤테로아릴렌기, 치환 또는 비치환된 C1-C10 알킬렌기이고, R 1 and R 2 are each independently a simple bond, -O-, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 1 -C 10 alkylene group,

Bp은 벤조페논 작용기로부터 유래된 1가 연결기이다.Bp is a monovalent linking group derived from a benzophenone functional group.

[화학식 II][Formula II]

Figure pat00035
Figure pat00035

상기 화학식에서, In the above formula,

n은 1 이상이고, n is 1 or more,

Ar'은 m차 연결기를 갖는 치환 또는 비치환된 C6-C60 아릴기, m차 연결기를 갖는 치환 또는 비치환된 C3-C60 헤테로아릴기 또는 m차 연결기를 갖는 치환 또는 비치환된 융합된 C6-C60 아릴기이고, Ar' is a substituted or unsubstituted C 6 -C 60 aryl group having an m-th linking group, a substituted or unsubstituted C 3 -C 60 heteroaryl group having an m-th linking group, or a substituted or unsubstituted having an m-th linking group A fused C 6 -C 60 aryl group,

R3 및 R4는 각각 독립적으로, 단순 결합, -O-, 치환 또는 비치환된 C6-C30아릴렌기, 치환 또는 비치환된 C3-C30 헤테로아릴렌기, 치환 또는 비치환된 C6-C30 융합된 아릴렌기, 치환 또는 비치환된 C1-C10 알킬렌기이고, R 3 and R 4 are each independently a simple bond, -O-, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 6 -C 30 fused arylene group, substituted or unsubstituted C 1 -C 10 alkylene group,

Bp'은 벤조페논 작용기로부터 유래된 1가 연결기이다.Bp' is a monovalent linking group derived from a benzophenone functional group.

상기 치환은 상기 아릴렌기, 헤테로아릴렌기, 알킬렌기, 알콕실렌기, 또는 아미드기의 탄소원자에 결합된 1개 이상의 수소원자가 C6-C30아릴, C3-C30헤테로아릴, C1-C10 알킬기 또는 P(X)2=0 화합물로 치환되어 이루어질 수 있고, 상기 X는 치환 또는 비치환된 C1-C10 알킬기 또는 치환 또는 비치환된 C3-C30 아릴렌기 또는 헤테로아릴렌기일 수 있으며, 구체적으로는 C1-C10 알킬기로 치환된 페닐일 수 있으며, 아미드기 또는 아민기의 질소원자에 결합된 1개 이상의 수소원자가 C6-C30아릴, C3-C30헤테로아릴 또는 C1-C10 알킬기로 치환되어 이루어질 수 있으며, 또한, 상기 아릴렌기, 헤테로아릴렌기, 알킬렌기, 알콕실렌기, 아미드기의 탄소원자, 또는 아미드기 또는 아민기의 질소원자 중 적어도 1개 이상이 산소로 치환될 수 있다.In the substitution, at least one hydrogen atom bonded to the carbon atom of the arylene group, heteroarylene group, alkylene group, alkoxyylene group, or amide group is C 6 -C 30 aryl, C 3 -C 30 heteroaryl, C 1- It may be formed by being substituted with a C 10 alkyl group or a P(X) 2 =0 compound, wherein X is a substituted or unsubstituted C 1 -C 10 alkyl group or a substituted or unsubstituted C 3 -C 30 arylene group or heteroarylene It may be a group, specifically , it may be a phenyl substituted with a C 1 -C 10 alkyl group, and at least one hydrogen atom bonded to the nitrogen atom of the amide group or the amine group is C 6 -C 30 aryl, C 3 -C 30 hetero It may be formed by being substituted with an aryl or C 1 -C 10 alkyl group, and at least one of the above arylene group, heteroarylene group, alkylene group, alkoxyylene group, carbon atom of amide group, or nitrogen atom of amide group or amine group More than one may be substituted with oxygen.

상기 아릴렌기 또는 헤테로아릴렌기는 단일 벤젠고리 구조(제1 구조), 또는 2개 이상의 벤젠고리가 서로 단순결합으로 연결된 구조(제2 구조), 융합된 구조(제3 구조), 질소 원자, 또는 규소 원자 등에 2 이상의 벤젠고리가 연결되어 있는 구조(제4 구조)일 수 있다. 또한, 상기 제1 내지 제4 구조 중 적어도 2 이상이 혼합되어 연결된 구조일 수도 있다, The arylene group or heteroarylene group has a single benzene ring structure (first structure), or a structure in which two or more benzene rings are connected by simple bonds (second structure), a fused structure (third structure), a nitrogen atom, or It may be a structure in which two or more benzene rings are connected to a silicon atom or the like (the fourth structure). In addition, it may be a structure in which at least two or more of the first to fourth structures are mixed and connected.

상기에서 Ar은 하기 화학식으로부터 선택된 1종 또는 그의 동족체 또는 그의 유사체로부터 유래된 것일 수 있다:In the above, Ar may be one selected from the following formula, or an analog thereof or an analog thereof:

Figure pat00036
Figure pat00036
Figure pat00037
Figure pat00037
Figure pat00038
Figure pat00038
Figure pat00039
Figure pat00039
Figure pat00040
Figure pat00040
Figure pat00041
Figure pat00041
Figure pat00042
Figure pat00042
Figure pat00043
Figure pat00043
Figure pat00044
Figure pat00044
Figure pat00045
Figure pat00045

보다 구체적으로, Ar 또는 Ar'의 비제한적인 예는 하기를 포함할 수 있으나, 이에 제한되는 것은 아니다.More specifically, non-limiting examples of Ar or Ar' may include the following, but are not limited thereto.

Figure pat00046
Figure pat00046
Figure pat00047
Figure pat00047
Figure pat00048
Figure pat00048
Figure pat00049
Figure pat00049
Figure pat00050
Figure pat00050
Figure pat00051
Figure pat00051
Figure pat00052
Figure pat00052
Figure pat00053
Figure pat00053
Figure pat00054
Figure pat00054
Figure pat00055
Figure pat00055
Figure pat00056
Figure pat00056

본 발명의 일 양태에서, 상기 벤조페논 작용기 함유 화합물의 비제한적인 예에는 하기 화학식 1 내지 11 중 어느 하나로 표시되는 화합물이 있으나, 이에 제한되는 것은 아니다.In one aspect of the present invention, a non-limiting example of the benzophenone functional group-containing compound includes a compound represented by any one of the following Formulas 1 to 11, but is not limited thereto.

[화학식 1][Formula 1]

Figure pat00057
Figure pat00057

[화학식 2][Formula 2]

Figure pat00058
Figure pat00058

[화학식 3][Formula 3]

Figure pat00059
Figure pat00059

[화학식 4][Formula 4]

Figure pat00060
Figure pat00060

[화학식 5][Formula 5]

Figure pat00061
Figure pat00061

[화학식 6][Formula 6]

Figure pat00062
Figure pat00062

(상기에서 n은 1 이상, 바람직하게는 1 내지 4이다)(In the above, n is 1 or more, preferably 1 to 4)

[화학식 7][Formula 7]

Figure pat00063
Figure pat00063

[화학식 8][Formula 8]

Figure pat00064
Figure pat00064

[화학식 9][Formula 9]

Figure pat00065
Figure pat00065

[화학식 10][Formula 10]

Figure pat00066
Figure pat00066

[화학식 11][Formula 11]

Figure pat00067
Figure pat00067

본 발명에 따른 벤조페논 작용기 함유 화합물은 유기물층 형성을 위한 광경화성 조성물에 포함될 수 있다. The benzophenone functional group-containing compound according to the present invention may be included in a photocurable composition for forming an organic material layer.

본 발명의 일 실시양태에서 상기 화학식 1 내지 6의 화합물의 광경화물은 정공수송능력을 가진 triphenyl group 등을 가지고 있어 정공수송층에 바람직하게 사용될 수 있으나, 이러한 용도에 한정되는 것은 아니다.In one embodiment of the present invention, the photocured product of the compound of Formulas 1 to 6 may be preferably used in the hole transport layer because it has a triphenyl group having hole transport capability, but is not limited to this use.

또한, 본 발명의 일 실시양태에서 상기 화학식 7 내지 11의 화합물의 광경화물은 전자 수송 능력을 가지는 피리딘, 트리아졸, 이미다졸과 같은 구조를 포함하고 있어 전자수송물질로 사용될 수 있으나, 이러한 용도에 한정되는 것은 아니다.In addition, in one embodiment of the present invention, the photocured product of the compound of Formulas 7 to 11 contains structures such as pyridine, triazole, and imidazole having electron transport ability, and thus can be used as an electron transport material, It is not limited.

상기 광경화성 조성물에 사용되는 용매로는 벤조페논 작용기 함유 화합물을 용해시킬 수 있는 것이면 특별히 한정되지 않는다. 구체적인 예로서, 클로로벤젠, N-메틸-2-피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세트아마이드, 디메틸술폭사이드, N,N-디에틸아세트아마이드, 감마-부티로락톤, 감마-발레로락톤, m-크레졸, 에틸렌글리콜 모노메틸에테르, 에틸렌글리콜 모노메틸에테르 아세테이트, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노에틸에테르 아세테이트, 에틸렌글리콜 모노부틸에테르, 에틸렌글리콜 모노부틸에테르 아세테이트, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노메틸에테르 아세테이트, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 모노에틸에테르 아세테이트, 프로필렌글리콜 모노프로필에테르, 프로필렌글리콜 모노프로필에테르 아세테이트, 프로필렌글리콜 모노부틸에테르, 프로필렌글리콜 모노부틸에테르 아세테이트, 프로필렌글리콜 디메틸에테르, 프로필렌글리콜 디에틸에테르, 프로필렌글리콜 디프로필틸에테르, 프로필렌글리콜 디부틸에테르, 젖산에틸, 젖산부틸, 시클로헥사논 및 시클로펜타논으로 이루어진 군에서 선택되는 1종 이상을 사용할 수 있다.The solvent used in the photocurable composition is not particularly limited as long as it can dissolve the benzophenone functional group-containing compound. As a specific example, chlorobenzene, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-diethylacetamide, gamma-butyro Lactone, gamma-valerolactone, m-cresol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl Ether acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyltyl ether, propylene glycol dibutyl ether, ethyl lactate, butyl lactate, cyclohexanone and at least one selected from the group consisting of cyclopentanone Can be used.

상기 광경화성 조성물은 벤조페논 작용기 함유 화합물 100 중량부를 기준으로 5 내지 40 중량부의 용매를 사용하는 것이 바람직하다. 상기 용매의 함량이 상기 범위를 만족하는 경우에, 적절한 점도가 되어 코팅시 매끄러운 표면을 얻을 수 있고, 원하는 두께 구현이 용이하며, 조액시 고른 혼합을 형성하는 것이 가능해 미세 패턴 형성을 위한 물성 구현이 가능하고, 기판과의 밀착력이 개선되며, 균일한 코팅성 및 원하는 막 두께를 얻을 수 있다. The photocurable composition preferably uses 5 to 40 parts by weight of a solvent based on 100 parts by weight of the benzophenone functional group-containing compound. When the content of the solvent satisfies the above range, it has an appropriate viscosity to obtain a smooth surface during coating, it is easy to implement the desired thickness, and it is possible to form an even mixture when the liquid is prepared, so that the physical properties for forming a fine pattern are realized. It is possible, the adhesion to the substrate is improved, and a uniform coating property and a desired film thickness can be obtained.

본 발명의 일 구현예에 따른 상기 광경화성 조성물은 패턴 특성 조절과 내열성 등의 박막 물성을 부여하기 위하여 아크릴 중합체 또는 측쇄에 아크릴 불포화 결합을 갖는 아크릴 중합체를 더 포함할 수 있다. 아크릴 중합체가 본 발명의 광경화성 조성물에 포함되는 경우, 상기 아크릴 중합체는 본 발명의 광경화성 조성물 100 중량부를 기준으로 5 내지 70 중량부의 양으로 포함될 수 있다. 아크릴 중합체가 상기 함량으로 포함되는 경우에 광경화 시간 측면에서 만족스러운 효과를 기대할 수 있다. The photocurable composition according to an embodiment of the present invention may further include an acrylic polymer or an acrylic polymer having an acrylic unsaturated bond in the side chain in order to control pattern characteristics and impart thin film properties such as heat resistance. When the acrylic polymer is included in the photocurable composition of the present invention, the acrylic polymer may be included in an amount of 5 to 70 parts by weight based on 100 parts by weight of the photocurable composition of the present invention. When the acrylic polymer is included in the above content, a satisfactory effect can be expected in terms of photocuring time.

사용가능한 아크릴 중합체는 하기에 기재된 단량체들을 포함하는 단량체들의 공중합체로서 단량체의 예로는, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 도데실(메타)아크릴레이트 및 헥사데실(메타)아크릴레이트,이소보닐(메타)아크릴레이트, 다만틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 벤질(메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 2-에톡시에틸(메타)아크릴레이트, 아크릴산, 메타아크릴산, 스틸렌, 아세톡시스틸렌, 글리시딜아크릴레이트, 글리시딜 메타아크릴레이트, 이타코닉산, 말레익산무수물, 말레익산모노알킬 에스터, 모노알킬 퓨말레이트, 3,4-에폭시부틸(메타)아크릴레이트,2,3-에폭시시클로헥실(메타)아크릴레이트,3,4-에폭시시클로헥실메틸(메타)아크릴레이트, 3-에틸옥세탄-3-메틸(메타)아크릴레이트, N-메틸말레이미드, N-부틸말레이미드, N-페닐말레이미드, (메타)아크릴아미드 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상을 중합하여 사용할 수 있다.The usable acrylic polymer is a copolymer of monomers including monomers described below. Examples of monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate and hexadecyl (meth) acrylate, isobonyl (meth) )Acrylate, damanethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, Acrylic acid, methacrylic acid, styrene, acetoxystyrene, glycidyl acrylate, glycidyl methacrylate, itaconic acid, maleic anhydride, maleic acid monoalkyl ester, monoalkyl fumalate, 3,4-epoxybutyl ( Meth)acrylate,2,3-epoxycyclohexyl(meth)acrylate,3,4-epoxycyclohexylmethyl(meth)acrylate, 3-ethyloxetane-3-methyl(meth)acrylate, N-methyl Maleimide, N-butylmaleimide, N-phenylmaleimide, (meth)acrylamide, and the like, and these may be used alone or in combination of two or more.

본 발명의 일 구현예에 따른 상기 광경화성 조성물은 필요에 따라, 적색, 녹색, 청색 및 블랙으로 이루어진 군으로부터 선택된 적어도 하나의 색재 안료를 더 포함할 수 있다. The photocurable composition according to an embodiment of the present invention may further include at least one colorant pigment selected from the group consisting of red, green, blue, and black, if necessary.

이때 첨가되는 컬러 색재 안료의 함량은 유기물층의 사용 조건에 적절하게 선택될 수 있으며, 예를 들면 상기 광경화성 조성물 100 중량부를 기준으로 1 내지 50 중량부, 더 바람직하게는 1 내지 20 중량부일 수 있다. 상기 색재 안료의 함량이 이러한 범위를 만족하는 경우, 얻어지는 컬러필터의 색순도 및 휘도 특성이 매우 우수할 수 있다. At this time, the content of the color material pigment added may be appropriately selected according to the conditions of use of the organic material layer, for example, 1 to 50 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the photocurable composition. . When the content of the color material pigment satisfies this range, the color purity and luminance characteristics of the obtained color filter may be very excellent.

본 발명에 따른 광경화성 조성물은 유리 기판 등의 기재상에 스핀코팅, 슬릿 스핀코팅, 롤 코팅, 다이 코팅, 커튼코팅과 같은 통상의 용액공정 방법을 이용하여 코팅될 수 있다. 이어서, 코팅물은 UV광에 노광된 후 및 현상 공정을 거쳐 필름으로 형성될 수 있다. The photocurable composition according to the present invention may be coated on a substrate such as a glass substrate using a conventional solution process method such as spin coating, slit spin coating, roll coating, die coating, and curtain coating. Subsequently, the coating may be formed into a film after being exposed to UV light and through a developing process.

상기 노광 공정에 있어서, 광조사 수단으로 조사되는 광원으로는 자외선광, 예를 들면 250 nm 내지 400 nm 파장 범위의 자외선광을 들 수 있다. 또한, 광원의 조사방법으로는 고압수은등, 크세논등, 카본아크등, 할로겐램프, 복사기용 냉음극관, LED, 반도체 레이저 등 공지의 수단을 사용할 수 있으나, 이에 제한되는 것은 아니다. 상기 광조사는 상온, 바람직하게는 20 내지 25 ℃에서 5 분 내지 120 분, 바람직하게는 5 분 내지 50 분동안 수행될 수 있다. 상기 광조사 시간이 상기 범위에 있는 경우에 광경화 측면에서 만족스러운 효과를 기대할 수 있다.In the exposure step, as a light source irradiated by the light irradiation means, ultraviolet light, for example, ultraviolet light in a wavelength range of 250 nm to 400 nm may be exemplified. In addition, as a method of irradiating the light source, known means such as a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a cold cathode tube for a copier, an LED, a semiconductor laser, etc. may be used, but are not limited thereto. The light irradiation may be performed at room temperature, preferably 20 to 25°C for 5 minutes to 120 minutes, preferably 5 minutes to 50 minutes. When the light irradiation time is within the above range, a satisfactory effect can be expected in terms of photocuring.

상기 현상 공정은 노광 공정을 거친 광경화성 필름으로부터 노광된 영역을 현상액을 이용해 제거함으로써 패턴을 형성하는 공정으로, 여기에 사용되는 현상액으로는 알칼리 금속 또는 알칼리 토금속의 수산화물, 탄산염, 탄산수소염, 암모니아수 4급 암모늄염과 같은 염기성 수용액을 사용할 수 있다. 테트라메틸 암모늄 수용액과 같은 암모니아 4급 암모늄 수용액이 특히 바람직하다.The developing process is a process of forming a pattern by removing the exposed area from the photocurable film that has undergone the exposure process with a developer, and as a developer used therein, an alkali metal or alkaline earth metal hydroxide, carbonate, hydrogen carbonate, ammonia water 4 Basic aqueous solutions such as quaternary ammonium salts can be used. Particularly preferred is an aqueous ammonia quaternary ammonium solution such as an aqueous tetramethyl ammonium solution.

상기 광경화성 조성물은 일 실시양태에서 아크릴 중합체, 그 밖에 당업계에서 통상적으로 사용되는 첨가제를 더 포함할 수 있다.In one embodiment, the photocurable composition may further include an acrylic polymer and other additives commonly used in the art.

본 발명의 광경화성 조성물은 별도의 광경화제를 포함하지 않는 것을 특징으로 한다. 별도의 광경화제가 사용되지 않기 때문에, 광경화후에 미반응된 광개시제 불순물에 의해 유기전자소자의 성능이 저하되는 문제가 방지될 수 있다.The photocurable composition of the present invention is characterized in that it does not contain a separate photocuring agent. Since a separate photocuring agent is not used, a problem in that the performance of the organic electronic device is deteriorated due to unreacted photoinitiator impurities after photocuring can be prevented.

본 발명에 따른 일 실시양태의 전체적인 공정은 본 발명의 벤조페논 작용기 함유 화합물을 포함하는 광경화성 조성물을 기판에 용액공정에 의해 코팅하는 단계; 및 자외선광을 1 내지 30 분 동안 조사하는 단계;를 포함할 수 있으며, 이후, 선택적으로, 현상 공정을 거쳐 70 내지 200 ℃에서 약 30 분 내지 2시간동안 후열처리할 수 있다. The overall process of an embodiment according to the present invention comprises the steps of coating a photocurable composition comprising the benzophenone functional group-containing compound of the present invention on a substrate by a solution process; And irradiating ultraviolet light for 1 to 30 minutes; and then, optionally, post heat treatment at 70 to 200° C. for about 30 minutes to 2 hours through a developing process.

상기로부터 형성된 유기물층은 유기전자소자에 사용될 수 있다. The organic material layer formed from the above may be used for an organic electronic device.

본 발명에서 제공되는 벤조페논 작용기 함유 화합물을 벤조페논 작용기 함유 고분자 화합물과 비교하면 하기와 같다:The benzophenone functional group-containing compound provided in the present invention is compared with the benzophenone functional group-containing polymer compound as follows:

(1) 벤조페논 작용기 함유 고분자 화합물은 유기용매에 용해가 잘 되는 물질이지만, 정확한 분자량으로 제조할 수 없고, 제조 과정에서 촉매와 같은 불순물을 제거하기가 어려워 일정한 성능의 소자를 제작하는 데 어려움이 있을 뿐 아니라 소자의 수명도 줄어들어 상업화하기가 곤란하다. 특히, 고분자의 곁가지에 벤조페논 작용기가 결합된 경우에는 광가교 후에 용매 저항성을 갖는 문제점이 발생한다. (1) Although the benzophenone functional group-containing polymer compound is a material that is well soluble in organic solvents, it cannot be manufactured with an accurate molecular weight, and it is difficult to remove impurities such as catalysts during the manufacturing process, making it difficult to manufacture a device with a certain performance. In addition, it is difficult to commercialize the device because the lifespan of the device is shortened. In particular, when a benzophenone functional group is bonded to a side branch of a polymer, a problem of solvent resistance occurs after photocrosslinking.

(2) 종래에, 단분자는 용매에 용해되지 않아 용액공정에 의해 다층 박막의 제조에 사용될 수 없는 것으로 알려졌으나, 본 발명에 따르면 상기 단분자에 벤조페논 작용기를 포함하는 곁가지를 부가시켜 용매에 용해가능하게 함으로써 용액공정에 사용할 수 있다. 이러한 화합물은 또한 상기 벤조페논 작용기가 광가교에 의해 가교된 후에는 용매에 용해되지 않게 된다.(2) Conventionally, it was known that a single molecule was not dissolved in a solvent and thus could not be used in the production of a multilayer thin film by a solution process, but according to the present invention, a side branch containing a benzophenone functional group was added to the By making it soluble, it can be used in a solution process. These compounds also become insoluble in the solvent after the benzophenone functional group is crosslinked by photocrosslinking.

(3) 벤조페논 작용기 함유 고분자 화합물과 벤조페논 작용기 함유 화합물은 박막 형성 후에 박막을 이루는 구조에서 차이를 갖는다. 벤조페논 작용기 함유 고분자 화합물은 주사슬 구조를 그대로 유지하는 단순한 구조를 가지고 있으나, 벤조페논 작용기 함유 화합물은 주사슬 자체가 결합을 이루는 형태를 가지고 있어, 형성되는 박막의 구조가 완전히 상이하다. 또한, 벤조페논 작용기 함유 화합물로부터 박막을 형성하는 경우에는 포함되는 벤조페논 작용기의 수에 따라 선형으로부터 방사형까지 다양한 형태로 박막의 구조를 만들 수 있어 활용도가 큰 이점이 있다.(3) The benzophenone functional group-containing polymer compound and the benzophenone functional group-containing compound have a difference in the structure of forming a thin film after the thin film is formed. The benzophenone functional group-containing polymer compound has a simple structure that maintains the main chain structure as it is, but the benzophenone functional group-containing compound has a form in which the main chain itself forms a bond, so the structure of the formed thin film is completely different. In addition, in the case of forming a thin film from a benzophenone functional group-containing compound, the thin film structure can be made in various forms from linear to radial depending on the number of benzophenone functional groups included, which has a great advantage in utilization.

(4) 또한, 벤조페논 작용기 함유 고분자 화합물은 유기 용매에 용해되더라도 분자량이 커서 점도가 높은 상태를 유지하여 잉크젯과 같은 공정에 사용하기 어려운 반면, 벤조페논 작용기 함유 화합물은 낮은 점도를 형성하여 잉크젯과 같은 공정에 사용이 유리한 이점을 갖는다.(4) In addition, the benzophenone functional group-containing polymer compound has a high molecular weight even when dissolved in an organic solvent, so it is difficult to use in processes such as inkjet because it is difficult to use in a process such as inkjet. Use in the same process has an advantageous advantage.

본 발명에 따르는 유기전자소자는, 제1전극; 제2전극; 및 상기 제1전극과 상기 제2전극 사이에 상기 유기물층을 구비한 것이다. An organic electronic device according to the present invention comprises: a first electrode; A second electrode; And the organic material layer between the first electrode and the second electrode.

본 발명의 일 실시양태에 있어서, 상기 유기전자소자는 유기발광소자(OLED), 유기태양전지, 유기광다이오드(OPD, Organic Photodiode), 광센서, 유기감광체(OPC) 및 유기트랜지스터(OTFT)로 이루어진 군으로부터 선택될 수 있다.In one embodiment of the present invention, the organic electronic device is an organic light emitting device (OLED), an organic solar cell, an organic photodiode (OPD), a photosensor, an organic photoconductor (OPC), and an organic transistor (OTFT). It may be selected from the group consisting of.

상기 유기물층은 전자 수송층일 수 있다. 한편, 상기 유기전자소자는, 정공 주입층, 정공 수송층, 전자 저지층, 발광층, 정공 저지층, 전자수송층 및 전자 주입층 중 하나 이상을 더 포함할 수 있으며, 본 발명에 따르는 유기물층이 정공 주입층, 정공 수송층, 전자 저지층, 발광층, 정공 저지층, 전자수송층 및 전자 주입층 중 하나 이상으로 사용될 수 있다.The organic material layer may be an electron transport layer. Meanwhile, the organic electronic device may further include at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and the organic material layer according to the present invention is a hole injection layer. , A hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

보다 구체적으로, 본 발명을 따르는 유기전자소자의 일 실시양태는 제1전극/정공 주입층/정공 수송층/발광층/전자 수송층/전자 주입층/제2전극의 구조를 갖는다. 또는, 본 발명을 따르는 유기전자소자는 제1전극/정공 주입층/발광층/전자 수송층/전자 주입층/제2전극으로 이루어진 구조를 갖거나, 제1전극/정공 주입층/정공 수송층/발광층/정공 저지층/전자 수송층/전자 주입층/제2전극으로 이루어진 구조를 가질 수 있으나, 이에 한정되는 것은 아니다. More specifically, an embodiment of the organic electronic device according to the present invention has a structure of a first electrode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/second electrode. Alternatively, the organic electronic device according to the present invention has a structure consisting of a first electrode/hole injection layer/light emitting layer/electron transport layer/electron injection layer/second electrode, or a first electrode/hole injection layer/hole transport layer/light emitting layer/ It may have a structure consisting of a hole blocking layer/electron transport layer/electron injection layer/second electrode, but is not limited thereto.

본 발명을 따르는 유기전자소자의 발광층은 적색, 녹색, 청색 또는 백색을 포함하는 인광 또는 형광 도펀트를 포함할 수 있다. 이 중, 상기 인광 도펀트는 Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb 및 Tm으로 이루어진 군으로부터 선택된 하나 이상의 원소를 포함하는 유기금속화합물일 수 있다.The emission layer of the organic electronic device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue, or white. Among them, the phosphorescent dopant may be an organometallic compound including at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, and Tm.

또한, 본 발명에서는 제 1 기판과; 상기 제 1 기판에 위치하는 구동 박막트랜지스터와; 상기 제 1 기판에 위치하며 상기 구동 박막트랜지스터에 연결되는 발광다이오드로서, 제 벤조페논 작용기 함유 화합물의 광경화물을 적어도 하나의 유기물층에 포함하는 유기전자소자와; 상기 유기전자소자를 덮고 상기 제 1 기판과 합착되는 제 2 기판을 포함하는 표시 장치가 제공된다. In addition, in the present invention, the first substrate; A driving thin film transistor positioned on the first substrate; An organic electronic device disposed on the first substrate and connected to the driving thin film transistor, the organic electronic device including a photocured product of a compound containing a first benzophenone functional group in at least one organic material layer; A display device is provided that covers the organic electronic device and includes a second substrate bonded to the first substrate.

이하, 유기전자소자의 제조 방법의 일 실시양태를 살펴보기로 한다.Hereinafter, an embodiment of a method for manufacturing an organic electronic device will be described.

먼저 기판 상부에 높은 일함수를 갖는 제1전극용 물질을 증착법 또는 스퍼터링법 등에 의해 형성하여 제1전극을 형성한다. First, a material for a first electrode having a high work function is formed on a substrate by a vapor deposition method or a sputtering method to form a first electrode.

상기 제1전극은 애노드(Anode) 또는 캐소드(cathode)일 수 있다. 여기에서 기판으로는 통상적인 유기전자소자에서 사용되는 기판을 사용하는데 기계적 강도, 열적 안정성, 투명성, 표면 평활성, 취급용이성 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판이 바람직하다. The first electrode may be an anode or a cathode. Here, as the substrate, a substrate used in a typical organic electronic device is used, and a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling and waterproofness is preferable.

제1전극용 물질로는 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO), Al, Mg, Ag 등을 사용할 수 있으나, 이에 한정되는 것은 아니다. 상기 제1전극은 투명 전극, 반투명 전극 또는 반사 전극으로 구비될 수 있다.As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), Al, Mg, Ag, etc. can be used, but are limited thereto. It does not become. The first electrode may be provided as a transparent electrode, a translucent electrode, or a reflective electrode.

다음으로, 상기 제1전극 상부에 정공 주입층(HIL)을 형성할 수 있다. 상기 정공 주입층은 본 발명에 따른 광경화성 조성물을 용액 공정에 의해 코팅하여 형성된 유기물층일 수 있다.Next, a hole injection layer HIL may be formed on the first electrode. The hole injection layer may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

상기 정공 주입층의 두께는 약 100Å 내지 10000Å, 바람직하게는 100Å 내지 1000 Å일 수 있다. 상기 정공 주입층의 두께가 100Å 미만인 경우, 정공주입 특성이 저하될 수 있으며, 상기 정공 주입층의 두께가 10000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. This is because when the thickness of the hole injection layer is less than 100 Å, hole injection characteristics may be deteriorated, and when the thickness of the hole injection layer exceeds 10000 Å, the driving voltage may increase.

다음으로 상기 정공주입층 상부에 정공 수송층(HTL)을 형성할 수 있다. 상기 정공수송층은 본 발명에 따른 광경화성 조성물을 용액 공정에 의해 코팅하여 형성된 유기물층일 수 있다.Next, a hole transport layer (HTL) may be formed on the hole injection layer. The hole transport layer may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

상기 정공 수송층의 두께는 약 50Å 내지 1000Å, 바람직하게는 100Å 내지 600Å일 수 있다. 상기 정공 수송층의 두께가 50Å 미만인 경우, 정공수송 특성이 저하될 수 있으며, 상기 정공 수송층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The thickness of the hole transport layer may be about 50 Å to 1000 Å, preferably 100 Å to 600 Å. This is because when the thickness of the hole transport layer is less than 50 Å, hole transport characteristics may be deteriorated, and when the thickness of the hole transport layer exceeds 1000 Å, the driving voltage may increase.

다음으로 상기 정공 수송층 상부에 발광층(EML)을 형성할 수 있다. 상기 발광층은 공지된 다양한 발광 물질을 이용하여 형성할 수 있다. 한편, 상기 발광층은 공지의 호스트 및 도펀트를 이용하여 형성할 수도 있으며, 도펀트의 경우, 공지의 형광 도펀트 및 공지의 인광 도펀트를 모두 사용할 수 있다.Next, an emission layer EML may be formed on the hole transport layer. The light-emitting layer may be formed using various known light-emitting materials. Meanwhile, the emission layer may be formed using a known host and dopant, and in the case of a dopant, both a known fluorescent dopant and a known phosphorescent dopant may be used.

예를 들어, 호스트로서는 Alq3, CBP(4,4'-N,N'-디카바졸-비페닐), PVK(폴리(n-비닐카바졸)) 또는 DSA(디스티릴 아릴렌) 등을 사용할 수 있으나 이에 한정되는 것은 아니다.For example, Alq3, CBP (4,4'-N,N'-dicarbazole-biphenyl), PVK (poly(n-vinylcarbazole)) or DSA (distyryl arylene) can be used as the host. However, it is not limited thereto.

도펀트의 경우, Ir(ppy)3 (ppy는 페닐피리딘의 약어임)(녹색), (4,6-F2ppy)2Irpic, PtOEP(platinum(II)octaethylporphyrin), 하기 구조식을 갖는 화합물, Firpric, TBPe 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.For dopants, Ir(ppy)3 (ppy is an abbreviation for phenylpyridine) (green), (4,6-F2ppy)2Irpic, PtOEP (platinum(II)octaethylporphyrin), a compound having the following structural formula, Firpric, TBPe, etc Can be used, but is not limited thereto.

Figure pat00068
Figure pat00068

Figure pat00069
Figure pat00069

Figure pat00070
Figure pat00070

상기 도펀트의 함량은 발광층 형성재료 100 중량부 (즉, 호스트와 도펀트의 총중량은 100중량부로 함)를 기준으로 하여 0.1 내지 20 중량부, 특히 0.5 ~ 12 중량부인 것이 바람직하다. 도펀트의 함량이 0.1 중량부 미만이면 도펀트 부가에 따른 효과가 미미하고 20 중량부를 초과하면 인광이나 형광 모두 다 농도 켄칭(quenching)과 같은 농도 소광이 일어나 바람직하지 못하다.The content of the dopant is preferably 0.1 to 20 parts by weight, particularly 0.5 to 12 parts by weight, based on 100 parts by weight of the light emitting layer forming material (ie, the total weight of the host and the dopant is 100 parts by weight). If the content of the dopant is less than 0.1 parts by weight, the effect of adding the dopant is insignificant, and if the content of the dopant exceeds 20 parts by weight, concentration quenching such as concentration quenching occurs in both phosphorescence and fluorescence, which is not preferable.

상기 발광층의 두께는 약 100Å 내지 1000Å, 바람직하게는 200Å 내지 600Å일 수 있다. 상기 발광층의 두께가 100Å 미만인 경우, 발광 특성이 저하될 수 있으며, 상기 발광층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The thickness of the emission layer may be about 100 Å to 1000 Å, preferably 200 Å to 600 Å. This is because when the thickness of the emission layer is less than 100 Å, the emission characteristics may be deteriorated, and when the thickness of the emission layer exceeds 1000 Å, the driving voltage may increase.

발광층이 인광 도펀트를 포함할 경우, 삼중항 여기자 또는 정공이 전자 수송층으로 확산되는 현상을 방지하기 위하여 정공 저지층(HBL)을 발광층 상부에 형성할 수 있다. 이 때 사용할 수 있는 정공 저지층 물질은 본 발명에 따른 광경화성 조성물을 용액 공정에 의해 코팅하여 형성된 유기물층일 수 있다.When the emission layer includes a phosphorescent dopant, a hole blocking layer (HBL) may be formed on the emission layer to prevent diffusion of triplet excitons or holes into the electron transport layer. The hole blocking layer material that can be used at this time may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

상기 정공 저지층의 두께는 약 50Å 내지 1000Å, 바람직하게는 100Å 내지 300Å일 수 있다. 상기 정공저지층의 두께가 50Å 미만인 경우, 정공저지 특성이 저하될 수 있으며, 상기 정공저지층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The thickness of the hole blocking layer may be about 50 Å to 1000 Å, preferably 100 Å to 300 Å. This is because when the thickness of the hole blocking layer is less than 50 Å, the hole blocking characteristics may be deteriorated, and when the thickness of the hole blocking layer exceeds 1000 Å, the driving voltage may increase.

다음으로 전자수송층(ETL)을 형성한다. 상기 전자수송층은 본 발명에 따른 광경화성 조성물을 용액 공정에 의해 코팅하여 형성된 유기물층일 수 있다.Next, an electron transport layer (ETL) is formed. The electron transport layer may be an organic material layer formed by coating the photocurable composition according to the present invention by a solution process.

상기 전자수송층의 두께는 약 100Å 내지 1000Å, 바람직하게는 100Å 내지 500Å일 수 있다. 상기 전자수송층의 두께가 100Å 미만인 경우, 전자수송 특성이 저하될 수 있으며, 상기 전자수송층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The thickness of the electron transport layer may be about 100 Å to 1000 Å, preferably 100 Å to 500 Å. This is because when the thickness of the electron transport layer is less than 100 Å, electron transport characteristics may be deteriorated, and when the thickness of the electron transport layer exceeds 1000 Å, the driving voltage may increase.

또한 전자수송층 상부에 음극으로부터 전자의 주입을 용이하게 하는 기능을 가지는 물질인 전자주입층(EIL)이 적층될 수 있다.In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer.

전자주입층으로서는 LiF, NaCl, CsF, Li2O, BaO 등과 같은 전자주입층 형성 재료로서 공지된 임의의 물질을 이용할 수 있다. 상기 전자주입층의 증착조건 및 코팅조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li 2 O, BaO or the like can be used. The deposition conditions and coating conditions of the electron injection layer vary depending on the compound to be used, but are generally selected from the same range of conditions as the formation of the hole injection layer.

상기 전자주입층의 두께는 약 1Å 내지 100Å, 바람직하게는 5Å 내지 90Å 일 수 있다. 상기 전자주입층의 두께가 1Å 미만인 경우, 전자주입 특성이 저하될 수 있으며, 상기 전자주입층의 두께가 100Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The thickness of the electron injection layer may be about 1 Å to 100 Å, preferably 5 Å to 90 Å. This is because when the thickness of the electron injection layer is less than 1 Å, electron injection characteristics may be deteriorated, and when the thickness of the electron injection layer exceeds 100 Å, the driving voltage may increase.

마지막으로 전자주입층 상부에 진공증착법이나 스퍼터링법 등의 방법을 이용하여 제2전극을 형성할 수 있다.Finally, the second electrode may be formed on the electron injection layer by using a method such as a vacuum deposition method or a sputtering method.

상기 제2전극은 캐소드 또는 애노드로 사용될 수 있다. 상기 제2전극 형성용 금속으로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로서는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag)등을 들 수 있다. 또한, 전면 발광 소자를 얻기 위하여 ITO, IZO를 사용한 투명 캐소드를 사용할 수도 있다.The second electrode may be used as a cathode or an anode. As the metal for forming the second electrode, a metal having a low work function, an alloy, an electrically conductive compound, and a mixture thereof may be used. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). Can be lifted. In addition, a transparent cathode using ITO or IZO may be used to obtain a top light emitting device.

본 발명을 실시예에 의거하여 더욱 상세하게 설명하면 다음과 같다. 그러나, 본 발명이 이에 한정되는 것은 아니다. The present invention will be described in more detail based on examples as follows. However, the present invention is not limited thereto.

제조예 1: 화학식 1의 화합물Preparation Example 1: Compound of Formula 1

Figure pat00071
Figure pat00071

중간체 (a)의 제조Preparation of intermediate (a)

2-목 둥근바닥 플라스크에 비스(4-브로모페닐)아민 (5 g, 0.0153 mol), 1-헵탄올 (1.6 mL ,0.0153 mol), 요오드화 제일구리 (0.08 eq), 포타슘 포스페이트 (3.8 g, 0.0612 mol), 트랜스-1,2-시클로헥산디아민 (2.2 mL, 0.0153 mol)을 넣고 1,4-디옥산(50 mL)을 넣었다. 110 ℃ 에서 24 시간동안 환류시켜 반응을 진행하였다. 디클로로메탄(MC)/물을 이용하여 Work up 하여 유기층을 분리하였다. 이어서, 증발시켜 용매를 제거하였다. 컬럼 (디클로로메탄 : 헥산 = 1:3 v/v)을 통해 정제하였다. 에탄올에 의해 제결정한 후에 여과하여 중간체 (a)를 수득하였다.In a two-neck round bottom flask, bis(4-bromophenyl)amine (5 g, 0.0153 mol), 1-heptanol (1.6 mL,0.0153 mol), cuprous iodide (0.08 eq), potassium phosphate (3.8 g, 0.0612 mol), trans-1,2-cyclohexanediamine (2.2 mL, 0.0153 mol) was added, and 1,4-dioxane (50 mL) was added. The reaction was carried out by refluxing at 110° C. for 24 hours. The organic layer was separated by working up using dichloromethane (MC)/water. Then, the solvent was removed by evaporation. It was purified through a column (dichloromethane: hexane = 1:3 v/v). After crystallizing with ethanol, it was filtered to obtain an intermediate (a).

중간체 (b)의 제조Preparation of intermediate (b)

질소분위기 하에서 100 mL 2-목 플라스크에 소듐 하이드라이드(0.048 g, 0.002 mol)를 넣고 1시간동안 교반하였다. (4-하이드록시페닐)(페닐)메타논 (1.63 g, 0.0086 mol)을 넣고 DMSO (10 mL) 에 녹인 후에, 천천히 적가하였다. 상기 물질을 모두 넣은 후에 중간체 (a) (3 g, 0.0086 mol)을 DMSO (30 ml) 에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응이 종료된 후에 에틸 아세테이트(EA)/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피로 정제하여 최종물질을 수득하였다.In a nitrogen atmosphere, sodium hydride (0.048 g, 0.002 mol) was added to a 100 mL 2-neck flask and stirred for 1 hour. (4-hydroxyphenyl)(phenyl)methanone (1.63 g, 0.0086 mol) was added and dissolved in DMSO (10 mL), and then slowly added dropwise. After all of the above substances were added, intermediate (a) (3 g, 0.0086 mol) was dissolved in DMSO (30 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After the reaction was completed, it was worked up with ethyl acetate (EA)/distilled water. The crude mixture was purified by column chromatography to obtain a final material.

화학식 1의 화합물의 제조Preparation of the compound of formula 1

2-목 둥근바닥 플라스크에 중간체 (b)(3 g, 0.006 mol), 트리스(4-브로모페닐)아민(0.93 g, 0.002 mol), 요오드화 제일구리(0.57 g, 0.003 mol), 포타슘 포스페이트(3.3 g, 0.03), 트랜스-1,2-시클로헥산 디아민 (1.9 mL, 0.0036 mol)을 넣고 1,4-디옥산(50 mL)을 넣었다. 110 ℃에서 24 시간동안 환류하여 반응을 진행하였다. 반응 종료 후에 Work up (디클로로메탄/물)하여 유기층을 분리하였다. 증발에 의해 용매를 감압 제거하였다. 컬럼으로 물질을 정제하였다. 에탄올에 의해 재결정한 후에 여과하여 최종물질을 수득하였다.In a two-neck round bottom flask, intermediate (b) (3 g, 0.006 mol), tris(4-bromophenyl)amine (0.93 g, 0.002 mol), cuprous iodide (0.57 g, 0.003 mol), potassium phosphate ( 3.3 g, 0.03), trans-1,2-cyclohexane diamine (1.9 mL, 0.0036 mol) was added, and 1,4-dioxane (50 mL) was added. The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, work up (dichloromethane/water) to separate the organic layer. The solvent was removed under reduced pressure by evaporation. The material was purified by column. After recrystallization with ethanol, it was filtered to obtain a final material.

1H NMR (CDCl3, 300 MHz); δ = 7.78-7.74 (m, -CH-), 7.64-7.55 (m, -CH-), 7.24 (d, -CH-), 6.76 (d, -CH-), 6.69-6.52(m, -CH-), 4.06 (t, -CH2-), 1.59 (t, -CH2-), 1.31-1.29 (s, -CH2- ), 0.88 (t, -CH3-)　 1 H NMR (CDCl 3 , 300 MHz); δ = 7.78-7.74 (m, -CH-), 7.64-7.55 (m, -CH-), 7.24 (d, -CH-), 6.76 (d, -CH-), 6.69-6.52 (m, -CH-) -), 4.06 (t, -CH 2 -), 1.59 (t, -CH 2 -), 1.31-1.29 (s, -CH 2- ), 0.88 (t, -CH 3 -)

제조예 2: 화학식 2의 화합물Preparation Example 2: Compound of Formula 2

Figure pat00072
Figure pat00072

중간체 (a)의 제조Preparation of intermediate (a)

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.19 g, 0.008 mol)를 넣고 1시간동안 교반시켰다. 3,6-디브로모-9H-카바졸 (3g, 0.0092 mol)을 넣고 DMSO (30 mL) 에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후에 이소펜틸보론산 (1 mL, 0.009 mol)을 DMSO (5 ml)에 녹여 첨가하였다. 80 ℃에서 24시간 반응을 진행하였다. 반응 종료 후 침전물을 필터하고, 여과액을 받아 용매를 감압제거하였다. Crude 상태의 혼합물을 컬럼 크로마토그래피로 정제하여 중간체 (b)을 수득하였다. (에틸 아세테이트:헥산 = 1: 20 v/v)In a nitrogen atmosphere, sodium hydride (0.19 g, 0.008 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. 3,6-dibromo-9H-carbazole (3g, 0.0092 mol) was added and dissolved in DMSO (30 mL), and then slowly added dropwise. After adding all the substances, isopentylboronic acid (1 mL, 0.009 mol) was dissolved in DMSO (5 ml) and added. The reaction was carried out at 80° C. for 24 hours. After the reaction was completed, the precipitate was filtered, the filtrate was collected, and the solvent was removed under reduced pressure. The crude mixture was purified by column chromatography to obtain an intermediate (b). (Ethyl acetate:hexane = 1: 20 v/v)

중간체 (b)의 제조Preparation of intermediate (b)

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.12 g, 0.004 mol)를 넣고 1시간동안 교반하였다. 중간체 (a) (1.5 g, 0.0047 mol)을 넣고 DMSO (10 mL) 에 녹인 후, 천천히 적가하였다. 중간체 (a)를 모두 넣은 후 (4-하이드록시페닐)(페닐)메타논 (0.94 g, 0.0047 mol)을 DMSO (10 ml)에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후에 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼 크로마토그래피(에틸 아세테이트:헥산 = 1: 20 v/v)로 정제하여 중간체 (b)를 수득하였다. In a nitrogen atmosphere, sodium hydride (0.12 g, 0.004 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. Intermediate (a) (1.5 g, 0.0047 mol) was added and dissolved in DMSO (10 mL), and then slowly added dropwise. After adding all of the intermediate (a), (4-hydroxyphenyl)(phenyl)methanone (0.94 g, 0.0047 mol) was dissolved in DMSO (10 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, it was worked up with ethyl acetate/distilled water. The crude mixture was purified by column chromatography (ethyl acetate:hexane = 1: 20 v/v) to obtain an intermediate (b).

화학식 2의 화합물의 제조Preparation of the compound of formula 2

질소분위기 하에서 250 mL 1목 플라스크에 중간체 (b) (1.1 g, 0.0025 mol), 트리스(4-브로모페닐)아민 (0.8 g 0.0008 mol), 포타슘 포스페이트 (2.3 g, 0.01 mol), CuI (0.2 g, 0.0015 mol ), 트랜스-1,2-디아미노시클로헥산 (0.32 mL, 0.0024 mol), 1,4-디옥산 (70 mL)을 넣었다. 80 ℃에서 48시간동안 반응을 진행 시켰다. 반응 종료 후에, ??칭하고 유기용매를 감압제거하였다. 고체 상태의 혼합물을 컬럼크로마토그래피(디클로로메탄 : 헥산 = 1: 7 v/v)로 정제하여 최종 물질인 화학식 2의 화합물을 수득하였다.Intermediate (b) (1.1 g, 0.0025 mol), tris(4-bromophenyl)amine (0.8 g 0.0008 mol), potassium phosphate (2.3 g, 0.01 mol), CuI (0.2 g, 0.0015 mol), trans-1,2-diaminocyclohexane (0.32 mL, 0.0024 mol), and 1,4-dioxane (70 mL) were added. The reaction was allowed to proceed at 80° C. for 48 hours. After completion of the reaction, quenching was performed and the organic solvent was removed under reduced pressure. The solid mixture was purified by column chromatography (dichloromethane: hexane = 1: 7 v/v) to obtain a final material, the compound of Formula 2.

1H NMR (CDCl3, 300 MHz); δ = 8.78 (s, -CH-), 7.84-7.74 (m, -CH-), 7.64-7.55 (m, -CH-), 7.37 (t, -CH-), 7.24(d, -CH-), 6.94 (d, -CH-), 6.63 (d, -CH), 2.62 (t, -CH2- ), 1.62-1.58 (m, -CH2-), 1.25 (m, -H-), 0.91 (d, -CH3) 1 H NMR (CDCl 3 , 300 MHz); δ = 8.78 (s, -CH-), 7.84-7.74 (m, -CH-), 7.64-7.55 (m, -CH-), 7.37 (t, -CH-), 7.24 (d, -CH-) , 6.94 (d, -CH-), 6.63 (d, -CH), 2.62 (t, -CH 2- ), 1.62-1.58 (m, -CH 2 -), 1.25 (m, -H-), 0.91 (d, -CH 3 )

제조예 3: 화학식 3의 화합물Preparation Example 3: Compound of Formula 3

Figure pat00073
Figure pat00073

중간체 (1)의 제조Preparation of intermediate (1)

질소 분위기 하에서 500 mL 둥근 바닥 플라스크에, 1,3,5-트리브로모벤젠 (7 g, 0.022 mol), 비스(피나콜레이토)디보론 (11.3 g, 0.044 mol), 포타슘 아세테이트 (6.4 g, 0.066 mol), Pd(pph3)4 (0.2g, 0.0002 mol)을 넣고 1,4-디옥산 (200 mL)를 넣어 교반시켰다. 110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 상온에서 식혀 에틸 아세테이트로 세척하였다. 여과액을 받아 용매를 모두 날린 후, 컬럼 크로마토그래피(에틸 아세테이트:헥산 =1:20 v/v)하여 중간체 (1)을 수득하였다.In a 500 mL round bottom flask under a nitrogen atmosphere, 1,3,5-tribromobenzene (7 g, 0.022 mol), bis(pinacollato)diboron (11.3 g, 0.044 mol), potassium acetate (6.4 g, 0.066 mol), Pd(pph 3 ) 4 (0.2g, 0.0002 mol) was added and 1,4-dioxane (200 mL) was added and stirred. The reaction was carried out by refluxing at 110°C for 24 hours. After the reaction was completed, it was cooled at room temperature and washed with ethyl acetate. After receiving the filtrate and removing all the solvent, the intermediate (1) was obtained by column chromatography (ethyl acetate:hexane =1:20 v/v).

중간체 (2)의 제조 Preparation of intermediate (2)

질소 분위기 하에서 250 mL 2-목 플라스크에, 중간체 (1) (2 g, 0.0049 mol), 1,4-디브로모벤젠 (2.3 g, 0.01 mol), Pd(pph3)4 (0.32 g, 0.00005 mol)를 넣고, THF (50 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 50 mL)을 넣었다. 80 ℃ 에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후에, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피 (에틸 아세테이트 : 헥산 = 1:8 v/v)로 정제하여 중간체 (2)을 수득하였다.In a 250 mL 2-neck flask under nitrogen atmosphere, intermediate (1) (2 g, 0.0049 mol), 1,4-dibromobenzene (2.3 g, 0.01 mol), Pd(pph 3 ) 4 (0.32 g, 0.00005 mol) was added, and THF (50 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 50 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvents in the separated organic layer were blown off, the mixture was purified by column chromatography (ethyl acetate: hexane = 1:8 v/v) to obtain an intermediate (2).

중간체 (3)의 제조Preparation of intermediate (3)

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.048 g, 0.002 mol)를 넣고 1시간동안 교반시켰다. (4-하이드록시페닐)(페닐)메타논 (3 g, 0.015 mol)을 넣고 DMSO (10 mL)에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후에 중간체 (2) (3.53 g, 0.0075 mol)을 DMSO (30 ml)에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후에 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피(에틸 아세테이트:헥산 = 1: 20 v/v)로 정제하여 중간체 (3) 을 수득하였다. In a nitrogen atmosphere, sodium hydride (0.048 g, 0.002 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. (4-hydroxyphenyl)(phenyl)methanone (3 g, 0.015 mol) was added and dissolved in DMSO (10 mL), and then slowly added dropwise. After all of the substances were added, the intermediate (2) (3.53 g, 0.0075 mol) was dissolved in DMSO (30 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, it was worked up with ethyl acetate/distilled water. The crude mixture was purified by column chromatography (ethyl acetate:hexane = 1: 20 v/v) to obtain an intermediate (3).

중간체 (a)의 제조Preparation of intermediate (a)

질소 분위기하에서 250 mL 둥근바닥 플라스크에 3,6-디브로모카바졸 (5 g, 0.015 mol), 1-브로모-4-데실벤젠 (2.4 mL, 0.015 mol), 요오드화 제일구리 (0.57 g, 0.003 mol), 포타슘 포스페이트 (6.4 g, 0.03 miol), 트랜스-1,2-시클로헥산 디아민 (1.7 mL, 0.015 mol)을 넣고 1,4-디옥산 (200 mL) 을 넣고 교반시켰다. 110 ℃ 에서 19시간 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식힌 후, 디클로로메탄/증류수로 추출하여 유기층을 분리시켰다. 유기층의 용매를 모두 날리고 에틸 아세테이트로 세척하였다. 여과액을 받아 에틸 아세테이트를 감압제거한 후, 컬럼크로마토그래피 (디클로로메탄:헥산 = 1: 10 v/v)로 중간체 (a)를 수득하였다.In a 250 mL round-bottom flask under nitrogen atmosphere, 3,6-dibromocarbazole (5 g, 0.015 mol), 1-bromo-4-decylbenzene (2.4 mL, 0.015 mol), cuprous iodide (0.57 g, 0.003 mol) mol), potassium phosphate (6.4 g, 0.03 miol), and trans-1,2-cyclohexane diamine (1.7 mL, 0.015 mol) were added, and 1,4-dioxane (200 mL) was added and stirred. The reaction was carried out by refluxing at 110° C. for 19 hours. After completion of the reaction, after cooling at room temperature, extraction was performed with dichloromethane/distilled water to separate the organic layer. All solvents in the organic layer were removed and washed with ethyl acetate. After receiving the filtrate and removing ethyl acetate under reduced pressure, intermediate (a) was obtained by column chromatography (dichloromethane:hexane = 1: 10 v/v).

중간체 (b)의 제조 Preparation of intermediate (b)

질소 분위기 하에서 250 mL 둥근 바닥 플라스크에, 중간체 (a) (2 g, 0.005 mol), 비스(피나콜레이토)디보론 (2.5 g, 0.01 mol), 포타슘 아세테이트 (0.5 g, 0.015 mol), Pd(pph3)4 (0.34g, 0.0005 mol) 을 넣고 1,4-디옥산 (100 mL)를 넣어 교반시켰다. 110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 상온에서 식혀 에틸 아세테이트로 세척하였다. 여과액을 받아 용매를 모두 날린 후, 컬럼 크로마토그래피로 (에틸 아세테이트:헥산 =1:10 v/v) 중간체 (b)을 수득하였다.In a 250 mL round bottom flask under a nitrogen atmosphere, intermediate (a) (2 g, 0.005 mol), bis(pinacollato) diboron (2.5 g, 0.01 mol), potassium acetate (0.5 g, 0.015 mol), Pd( pph 3 ) 4 (0.34g, 0.0005 mol) was added and 1,4-dioxane (100 mL) was added and stirred. The reaction was carried out by refluxing at 110° C. for 24 hours. After the reaction was completed, it was cooled at room temperature and washed with ethyl acetate. After taking the filtrate and removing all the solvent, the intermediate (b) was obtained by column chromatography (ethyl acetate:hexane =1:10 v/v).

화학식 3의 화합물의 제조 Preparation of the compound of formula 3

질소 분위기 하에서 500 mL 2-목 플라스크에, 중간체 (b) (1 g, 0.002 mol), 중간체 (3) (2.8 g, 0.004 mol), Pd(pph3)4 (0.2 g, 0.00002 mol)를 넣고, THF (100 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 100 mL)을 넣었다. 80 ℃에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피 (디클로로메탄:헥산 = 1:4 v/v)로 정제하여 최종물질인 화학식 3의 화합물을 수득하였다.In a 500 mL 2-neck flask under a nitrogen atmosphere, intermediate (b) (1 g, 0.002 mol), intermediate (3) (2.8 g, 0.004 mol), and Pd(pph 3 ) 4 (0.2 g, 0.00002 mol) were added. , THF (100 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 100 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvent in the separated organic layer was blown off, the mixture was purified by column chromatography (dichloromethane:hexane = 1:4 v/v) to obtain a final material, the compound of Formula 3.

1H NMR (CDCl3, 300 MHz); δ = 7.93 (d, -CH-), 7.78-7.54 (m, -CH-), 7.35 (s, -CH-), 7.24-7.18 (m, -CH-), 6.98(t, -CH-), 6.76-6.51 (m, -CH-), 2.34 (s, -CH3), 1.87 (t, -CH2- ), 1.29 (s, -CH2-), 0.88 (d, -CH3) 1 H NMR (CDCl 3 , 300 MHz); δ = 7.93 (d, -CH-), 7.78-7.54 (m, -CH-), 7.35 (s, -CH-), 7.24-7.18 (m, -CH-), 6.98 (t, -CH-) , 6.76-6.51 (m, -CH-), 2.34 (s, -CH 3 ), 1.87 (t, -CH 2- ), 1.29 (s, -CH 2 -), 0.88 (d, -CH 3 )

제조예 4: 화학식 4의 화합물의 제조Preparation Example 4: Preparation of the compound of Formula 4

Figure pat00074
Figure pat00074

중간체 (1)의 제조Preparation of intermediate (1)

질소 분위기 하에서 500 mL 둥근 바닥 플라스크에, (4-아미노페닐)보론산 (5 g, 0.0365 mol), 4-브로모아닐린 (6.28 g, 0.0365 mol), Pd(pph3)4 (0.42 g, 0.000365 mol) 을 넣고 THF (50 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액(2N, 50 mL)을 넣었다. 80 ℃에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 중간체 (1)을 수득하였다.In a 500 mL round bottom flask under nitrogen atmosphere, (4-aminophenyl) boronic acid (5 g, 0.0365 mol), 4-bromoaniline (6.28 g, 0.0365 mol), Pd(pph 3 ) 4 (0.42 g, 0.000365) mol) was added and THF (50 mL) was added thereto, followed by stirring. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 50 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvent of the separated organic layer was blown away, the intermediate (1) was obtained by purification by column chromatography.

중간체 (2)의 제조Preparation of intermediate (2)

질소 분위기 하에서 250 mL 2-목 플라스크에, (4-하이드록시페닐)(페닐)메타논 (5 g, 0.025 mol), 3-브로모프로판-1-올 (3.5 mL, 0.025 mol), 포타슘 포스페이트 (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol)를 넣고 DSMO (100 mL)를 넣었다. 110 ℃ 에서 24시간 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 중간체 (2)를 수득하였다.In a 250 mL 2-neck flask under a nitrogen atmosphere, (4-hydroxyphenyl)(phenyl)methanone (5 g, 0.025 mol), 3-bromopropan-1-ol (3.5 mL, 0.025 mol), potassium phosphate (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol) was added and DSMO (100 mL) was added. The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvents in the separated organic layer were blown away, the intermediate was purified by column chromatography to obtain an intermediate (2).

중간체 (3)의 제조Preparation of intermediate (3)

질소 분위기 하에서 250 mL 2-목 플라스크에, 2,7-디브로모-9,9-디메틸-9H-플루오렌 (5 g, 0.014 mol), 중간체 (2) (1.8 g, 0,007 mol), 포타슘 포스페이트 (7.43 g, 0.035 mol), CuI (0.266 g, 0.0014 mol)를 넣고 DSMO (70 mL)를 넣었다. 110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 중간체 (3)을 수득하였다.In a 250 mL 2-neck flask under nitrogen atmosphere, 2,7-dibromo-9,9-dimethyl-9H-fluorene (5 g, 0.014 mol), intermediate (2) (1.8 g, 0,007 mol), potassium Phosphate (7.43 g, 0.035 mol), CuI (0.266 g, 0.0014 mol) was added, and DSMO (70 mL) was added. The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvent of the separated organic layer was blown away, the intermediate (3) was obtained by purification by column chromatography.

화학식 4의 화합물의 제조Preparation of the compound of formula 4

질소 분위기 하에서 250 mL 2-목 플라스크에, 중간체 (1) (1 g, 0.0054 mol), 중간체 (2) (5.7 g, 0.011 mol), 2-프로판올 (0.32 mL, 0.0054 mol), Pd(pph3)4 (0.06 g, 0.00005 mol) 를 넣고 1,2-디메톡시에탄 (60 mL)을 넣었다. 80 ℃에서 15시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 디클로로메탄/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 최종물질을 수득하였다.In a 250 mL 2-neck flask under nitrogen atmosphere, intermediate (1) (1 g, 0.0054 mol), intermediate (2) (5.7 g, 0.011 mol), 2-propanol (0.32 mL, 0.0054 mol), Pd(pph 3) ) 4 (0.06 g, 0.00005 mol) was added and 1,2-dimethoxyethane (60 mL) was added. The reaction was carried out by refluxing at 80° C. for 15 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with dichloromethane/distilled water to separate the organic layer. After all the solvent in the separated organic layer was blown off, the final material was obtained by purification by column chromatography.

1H NMR (CDCl3, 300 MHz); δ = 7.78-7.76 (m, -CH-), 7.64-7.54 (m, -CH-), 7.30 (d, -CH-), 7.06 (m, -CH-), 6.89 (m, -CH-), 6.69 (t, -CH-)　, 6.58 (m, -CH-), 4.29 (t, -CH2-), 4.06 (t, -CH2-), 2.25 (m, -CH2-), 1.89 (t, -CH2-), 1.72 (s, -CH3) 1 H NMR (CDCl 3 , 300 MHz); δ = 7.78-7.76 (m, -CH-), 7.64-7.54 (m, -CH-), 7.30 (d, -CH-), 7.06 (m, -CH-), 6.89 (m, -CH-) , 6.69 (t, -CH-), 6.58 (m, -CH-), 4.29 (t, -CH 2 -), 4.06 (t, -CH 2 -), 2.25 (m, -CH 2 -), 1.89 (t, -CH 2 -), 1.72 (s, -CH 3 )

제조예 5: 화학식 5의 화합물Preparation Example 5: Compound of Formula 5

Figure pat00075
Figure pat00075

중간체 (a)의 제조Preparation of intermediate (a)

100 ml 2-목 둥근바닥 플라스크를 호일로 감싸 빛이 들어가지 않게 한 뒤 디페닐포스핀 클로라이드 (5 g, 0.02 mol), DMF (15 ml) 를 넣고 질소 퍼징하였다. 에틸렌 글리콜:에탄올=9:1 v/v로 맞춘 뒤 드라이아이스 bath에 넣어 -20 ℃가 되도록 하고 NBS(3.7 g, 0.02 mol)를 넣었다. 4 시간동안 -20 ℃ 에서 교반하였다. 빙수(Ice water)에 ??칭시킨 후 실온(RT)으로 온도가 올라갈 때까지 교반하였다. 여과한 후에 메탄올로 세척하고, 이후 건조하여 중간체 (a)를 수득하였다.A 100 ml two-neck round bottom flask was wrapped with foil to prevent light from entering, and then diphenylphosphine chloride (5 g, 0.02 mol) and DMF (15 ml) were added and purged with nitrogen. Ethylene glycol: ethanol = 9:1 v/v was adjusted and put in a dry ice bath to reach -20°C, and NBS (3.7 g, 0.02 mol) was added. The mixture was stirred at -20°C for 4 hours. After quenching in ice water, the mixture was stirred until the temperature rises to room temperature (RT). After filtration, it was washed with methanol, and then dried to obtain an intermediate (a).

중간체 (b)의 제조Preparation of intermediate (b)

2-목 둥근바닥 플라스크에 2,7-디브로모-9,9′'-스피로바이플루오렌 (3 g, 0.0063 mol)을 넣고 탈수 디에틸 에테르 (20 mL)를 넣었다. -78 ℃ 로 맞춘 뒤 n-부틸 리튬 (0.8 mL, 0.0016 mol eq)을 넣어 준 후 3시간동안 교반하여 반응을 진행하였다. 중간체 (a) (5.4 g, 0.014 mol)을 넣고 실온(RT)에서 12시간 정도 교반하였다. 수조(Water bath)에 반응물을 ??칭시킨 후 디에틸 에테르로 추출하였다. 컬럼(헥산)으로 정제하여 중간체 (b)를 수득하였다.2,7-dibromo-9,9''-spirobifluorene (3 g, 0.0063 mol) was added to a 2-neck round bottom flask, and dehydrated diethyl ether (20 mL) was added. After the temperature was adjusted to -78 °C, n-butyl lithium (0.8 mL, 0.0016 mol eq) was added, followed by stirring for 3 hours to proceed with the reaction. Intermediate (a) (5.4 g, 0.014 mol) was added and stirred at room temperature (RT) for about 12 hours. After quenching the reaction product in a water bath (water bath) was extracted with diethyl ether. Purified by column (hexane) to obtain an intermediate (b).

중간체 (c)의 제조Preparation of intermediate (c)

100 ml 2-목 둥근바닥 플라스크에 중간체 (b )(2 g, 0.002mol), 헥실보론산 피나콜 에스테르 (2 g , 0.0097mol)을 넣고, THF (15 ml) 를 넣고 질소 퍼징하였다. 포타슘 카보네이트 (2 N, 12 ml)를 넣었다. Pd(PPh3)4 (테트라키스 팔라듐) (0.04 g, 0.038 mol) 을 넣었다. 약 10분 동안 디개싱(degassing)하였다. 80 ℃ 에서 overnight 반응을 진행하였다. 반응 종료 후, Work up (디클로로메탄/물)하여 유기층을 분리하였다. 컬럼하여 중간체 (c)를 수득하였다.In a 100 ml two-neck round bottom flask, intermediate (b) (2 g, 0.002 mol), hexylboronic acid pinacol ester (2 g, 0.0097 mol) was added, THF (15 ml) was added, followed by purging with nitrogen. Potassium carbonate (2 N, 12 ml) was added. Pd(PPh 3 ) 4 (tetrakis palladium) (0.04 g, 0.038 mol) was added. Degassed for about 10 minutes. The reaction was carried out overnight at 80 °C. After completion of the reaction, work up (dichloromethane/water) to separate the organic layer. By column, the intermediate (c) was obtained.

중간체 (d)의 제조 Preparation of intermediate (d)

100 ml 2-목 둥근바닥 플라스크를 호일로 감싸 빛이 들어가지 않게 한 뒤 중간체 (c) (2 g, 0.002 mol), DMF (15 ml) 를 넣고 질소 퍼징하였다. (에틸렌 글리콜:에탄올=9:1 v/v)로 맞춘 뒤 드라이아이스를 넣어 -20 ℃가 되도록 한 후, NBS(0.33 g, 0.002 mol)를 넣었다. 약 4 시간동안 -20 ℃ 에서 교반하여 반응을 진행하였다. 빙수에 ??칭시킨 후 실온(RT)으로 온도가 올라갈 때까지 교반하였다. 여과한 후 메탄올로 세척한 후 건조하여 중간체 (d)를 수득하였다.A 100 ml two-neck round bottom flask was wrapped with foil to prevent light from entering, and then intermediate (c) (2 g, 0.002 mol) and DMF (15 ml) were added and purged with nitrogen. (Ethylene glycol: ethanol = 9: 1 v/v), dry ice was added to make it -20 °C, and then NBS (0.33 g, 0.002 mol) was added. The reaction was carried out by stirring at -20°C for about 4 hours. After quenching in ice water, the mixture was stirred until the temperature rises to room temperature (RT). After filtering, washing with methanol and drying to obtain an intermediate (d).

화학식 5의 화합물의 제조Preparation of the compound of formula 5

질소분위기 하에 100 mL 2목 플라스크에 소듐 하이드라이드 (0.048 g, 0.002 mol)를 넣고 1시간동안 교반시켰다. (4-하이드록시페닐)(페닐)메타논 (1.3 g, 0.0033 mol)을 넣고 DMSO (10 mL) 에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후 중간체 (b) (2 g, 0.0016 mol)을 DMSO (30 ml) 에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피로 정제하여 최종물질을 수득하였다.Sodium hydride (0.048 g, 0.002 mol) was added to a 100 mL two-necked flask under a nitrogen atmosphere and stirred for 1 hour. (4-hydroxyphenyl)(phenyl)methanone (1.3 g, 0.0033 mol) was added and dissolved in DMSO (10 mL), and then slowly added dropwise. After all the substances were added, intermediate (b) (2 g, 0.0016 mol) was dissolved in DMSO (30 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, work up was performed with ethyl acetate/distilled water. The crude mixture was purified by column chromatography to obtain a final material.

1H NMR (CDCl3, 300 MHz); δ = 7.79-7.55 (m, -CH-), 7.64 (m, -CH-), 7.29-7.24 (m, -CH-), 7.01 (s, -CH-), 6.98(m, -CH-), 2.62 (t, -CH2-), 1.59 (t, -CH2-), 1.31-1.29 (s, -CH2- ), 0.88 (t, -CH3-)　 1 H NMR (CDCl 3 , 300 MHz); δ = 7.79-7.55 (m, -CH-), 7.64 (m, -CH-), 7.29-7.24 (m, -CH-), 7.01 (s, -CH-), 6.98 (m, -CH-) , 2.62 (t, -CH 2 -), 1.59 (t, -CH 2 -), 1.31-1.29 (s, -CH 2- ), 0.88 (t, -CH 3 -)

제조예 6: 화학식 6의 화합물의 제조 Preparation Example 6: Preparation of the compound of Formula 6

Figure pat00076
Figure pat00076

중간체 (a)의 제조Preparation of intermediate (a)

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.048 g, 0.002 mol)를 넣고 1시간동안 교반시켰다. (4-하이드록시페닐)(페닐)메타논 (5 g, 0.025 mol)을 넣고 DMSO (30 mL) 에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후 1,4-디브로모벤젠 (5.89 g, 0.025 mol)을 DMSO (30 ml) 에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후에 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피(에틸 아세테이트:헥산 = 1: 20 v/v)로 정제하여 중간체 (b)를 수득하였다. In a nitrogen atmosphere, sodium hydride (0.048 g, 0.002 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. (4-hydroxyphenyl)(phenyl)methanone (5 g, 0.025 mol) was added and dissolved in DMSO (30 mL), and then slowly added dropwise. After adding all the substances, 1,4-dibromobenzene (5.89 g, 0.025 mol) was dissolved in DMSO (30 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, it was worked up with ethyl acetate/distilled water. The crude mixture was purified by column chromatography (ethyl acetate:hexane = 1: 20 v/v) to obtain an intermediate (b).

중간체 (b)의 제조Preparation of intermediate (b)

질소 분위기하에서 250 mL 둥근바닥 플라스크에 중간체 (b) (1.2 g, 0.0036 mol), 비스(4-브로모페닐)아민 (1.2 g, 0.0036 mol), 요오드화 제일구리 (0.57 g, 0.003 mol), 포타슘 포스페이트 (3.3 g, 0.03), 트랜스-1,2-시클로헥산 디아민 (1.9 mL, 0.0036 mol)을 넣고 1,4-디옥산 (50 mL) 을 넣고 교반시켰다. 110 ℃ 에서 19시간 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식힌 후, 디클로로메탄/증류수로 추출하여 유기층을 분리시켰다. 유기층의 용매를 모두 날리고 에틸 아세테이트로 세척하였다. 여과액을 받아 에틸 아세테이트를 감압제거한 후, 컬럼크로마토그래피 (디클로로메탄:헥산 = 1: 10)로 중간체 (c)를 수득하였다. 수율: 1.4 g (66 %)In a 250 mL round bottom flask under nitrogen atmosphere, intermediate (b) (1.2 g, 0.0036 mol), bis(4-bromophenyl)amine (1.2 g, 0.0036 mol), cuprous iodide (0.57 g, 0.003 mol), potassium Phosphate (3.3 g, 0.03), trans-1,2-cyclohexane diamine (1.9 mL, 0.0036 mol) was added thereto, and 1,4-dioxane (50 mL) was added thereto, followed by stirring. The reaction was carried out by refluxing at 110° C. for 19 hours. After completion of the reaction, after cooling at room temperature, extraction was performed with dichloromethane/distilled water to separate the organic layer. All solvents in the organic layer were removed and washed with ethyl acetate. After receiving the filtrate and removing ethyl acetate under reduced pressure, the intermediate (c) was obtained by column chromatography (dichloromethane:hexane = 1: 10). Yield: 1.4 g (66 %)

화학식 6의 화합물의 제조Preparation of the compound of formula 6

질소분위기 하에서 500 mL 1목 플라스크에 중간체 (b) (1.5 g, 0.0025 mol), 2,7-비스(4,4,5,5-테트라메틸-1,3,2-디옥사보롤란-2-일)-9,9-디-n-옥틸플루오렌(1.6 g , 0.0025 mol), Pd(pph3)4 (0.03 g, 0.000026 mol)을 넣고 THF (30 mL)를 넣어 교반하였다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 30 mL)를 넣었다. 80 ℃ 에서 12시간동안 환류하여 반응을 진행하였다. MeOH에 반응물을 천천히 적가(drop)하여 침전시켰다. Intermediate (b) (1.5 g, 0.0025 mol), 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2) in a 500 mL 1-neck flask under nitrogen atmosphere -Yl)-9,9-di-n-octylfluorene (1.6 g, 0.0025 mol), Pd(pph 3 ) 4 (0.03 g, 0.000026 mol) was added, and THF (30 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 30 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours. The reactant was slowly added dropwise to MeOH to precipitate.

1H NMR (CDCl3, 300 MHz); δ = 7.93 (d, -CH-), 7.78-7.54 (m, -CH-), 7.35 (s, -CH-), 7.24-7.18 (m, -CH-), 6.98(t, -CH-), 6.76-6.51 (m, -CH-), 2.34 (s, -CH3), 1.87 (t, -CH2-), 1.29 (s, -CH2-), 0.88 (d, -CH3) 1 H NMR (CDCl 3 , 300 MHz); δ = 7.93 (d, -CH-), 7.78-7.54 (m, -CH-), 7.35 (s, -CH-), 7.24-7.18 (m, -CH-), 6.98 (t, -CH-) , 6.76-6.51 (m, -CH-), 2.34 (s, -CH 3 ), 1.87 (t, -CH 2 -), 1.29 (s, -CH 2 -), 0.88 (d, -CH 3 )

제조예 7: 화학식 7의 화합물의 제조Preparation Example 7: Preparation of the compound of Formula 7

Figure pat00077
Figure pat00077

중간체 (1)의 제조Preparation of intermediate (1)

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.048 g, 0.002 mol)를 넣고 1시간동안 교반시켰다. 1,3,5-트리브로모벤젠 (5 g, 0.0158 mol)을 넣고 DMSO (30 mL)에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후 3-메틸부탄-1-올 (1.4 mL, 0.0158 mol)을 DMSO (5 ml)에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피로 정제하여 중간체 (1)를 수득하였다.In a nitrogen atmosphere, sodium hydride (0.048 g, 0.002 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. 1,3,5-tribromobenzene (5 g, 0.0158 mol) was added and dissolved in DMSO (30 mL), and then slowly added dropwise. After adding all the substances, 3-methylbutan-1-ol (1.4 mL, 0.0158 mol) was dissolved in DMSO (5 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, work up was performed with ethyl acetate/distilled water. The crude mixture was purified by column chromatography to obtain an intermediate (1).

중간체 (2)의 제조Preparation of intermediate (2)

질소 분위기 하에서 500 mL 둥근 바닥 플라스크에, 중간체 (1) (3.5 g, 0.01 mol), 비스(피나콜레이토)디보론 (6.9 g, 0.027 mol), 포타슘 아세테이트 (3.9 g, 0.04 mol), Pd(pph3)4 (0.2g, 0.0002 mol)을 넣고 1,4-디옥산 (100 mL)를 넣어 교반시켰다. 110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 상온에서 식혀 에틸 아세테이트로 세척하였다. 여과액을 받아 용매를 모두 날린 후, 컬럼 크로마토그래피로 중간체(2)를 수득하였다.In a 500 mL round-bottom flask under nitrogen atmosphere, intermediate (1) (3.5 g, 0.01 mol), bis(pinacollato) diboron (6.9 g, 0.027 mol), potassium acetate (3.9 g, 0.04 mol), Pd( pph 3 ) 4 (0.2g, 0.0002 mol) was added and 1,4-dioxane (100 mL) was added and stirred. The reaction was carried out by refluxing at 110° C. for 24 hours. After the reaction was completed, it was cooled at room temperature and washed with ethyl acetate. After receiving the filtrate and removing all the solvent, the intermediate (2) was obtained by column chromatography.

중간체 (3)의 제조Preparation of intermediate (3)

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.039 g, 0.001 mol)를 넣고 1시간동안 교반시켰다. (5-브로모피리딘-3-일)보론산 (5 g, 0.0248 mol)을 넣고 DMSO (30 mL)에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후 (4-하이드록시페닐)(페닐)메타논 (4.9 g , 0.0248 mol)을 DMSO (30 ml)에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피로 정제하여 중간체 (3)을 수득하였다. In a nitrogen atmosphere, sodium hydride (0.039 g, 0.001 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. (5-bromopyridin-3-yl) boronic acid (5 g, 0.0248 mol) was added and dissolved in DMSO (30 mL), and then slowly added dropwise. After all the substances were added, (4-hydroxyphenyl)(phenyl)methanone (4.9 g, 0.0248 mol) was dissolved in DMSO (30 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, work up was performed with ethyl acetate/distilled water. The crude mixture was purified by column chromatography to obtain an intermediate (3).

중간체 (4)의 제조Preparation of intermediate (4)

질소 분위기 하에서 500 mL 2-목 플라스크에 3-브로모피리딘 (10 g, 0.0633 mol), 비스(피나콜레이토)디보론 (16 g, 0.0633 mol), Pd(pph3)4 (3.6 g, 0.003 mol), 포타슘 아세테이트 (18.5 g, 0.19mol)을 넣고 1,4-디옥산 (300 mL)를 넣어 교반 시켰다. 80 ℃ 에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 상온에서 식혀 에틸 아세테이트로 세척한 후, 여과액을 받아 컬럼크로마토그래피로 순수한 중간체(4)를 수득하였다.In a 500 mL 2-neck flask under nitrogen atmosphere, 3-bromopyridine (10 g, 0.0633 mol), bis(pinacollato) diboron (16 g, 0.0633 mol), Pd(pph 3 ) 4 (3.6 g, 0.003) mol), potassium acetate (18.5 g, 0.19 mol) was added, and 1,4-dioxane (300 mL) was added and stirred. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature, washed with ethyl acetate, and the filtrate was collected and purified by column chromatography to obtain a pure intermediate (4).

중간체 (5)의 제조Preparation of intermediate (5)

질소 분위기 하에서 500 mL 2-목 플라스크에 정제한 (1)번 중간체 (11 g, 0.05 mol), 1,3,5-트리브로모벤젠(19 g, 0.06 mol), Pd(pph3)4 (2.8 g, 0.0025 mol)을 넣고 THF (150 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액(2N, 150 mL)을 넣어 함께 교반시켰다. 80 ℃에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 컬럼크로마토그래피로 순수한 중간체 (5)를 수득하였다.Intermediate No. (1) purified in a 500 mL 2-neck flask under nitrogen atmosphere (11 g, 0.05 mol), 1,3,5-tribromobenzene (19 g, 0.06 mol), Pd(pph 3 ) 4 ( 2.8 g, 0.0025 mol) was added and THF (150 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 150 mL) was added and stirred together. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, pure intermediate (5) was obtained by column chromatography.

중간체 (6)의 제조Preparation of intermediate (6)

질소분위기 하에서 500 mL 2-목 플라스크에, 정제한 중간체(5) (8 g, 0.025 mol), 중간체 (3) (5.14 g, 0.013 mol), Pd(pph3)4 (2.8 g, 0.0025 mol)를 넣고, THF (150 mL) 을 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 150 mL)을 넣어 교반시켰다. 80 ℃에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후에 컬럼크로마토그래피로 순수한 중간체 (6)를 수득하였다.In a 500 mL 2-neck flask under nitrogen atmosphere, the purified intermediate (5) (8 g, 0.025 mol), intermediate (3) (5.14 g, 0.013 mol), Pd(pph 3 ) 4 (2.8 g, 0.0025 mol) Then, THF (150 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 150 mL) was added and stirred. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, pure intermediate (6) was obtained by column chromatography.

화학식 7의 화합물의 제조Preparation of the compound of formula 7

질소 분위기 하에서 250 mL 2-목 플라스크에, 중간체 (6) (2 g, 0.0032 mol), 중간체 (3) (2 g, 0.006 mol), 2-프로판올 (0.13 mL, 0.003 mol), Pd(pph3)4 (0.03 g, 0.00003 mol) 를 넣고 1,2-디메톡시에탄 (50 mL)을 넣었다. 80 ℃에서 15시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 디클로로메탄/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 최종물질을 수득하였다.In a 250 mL 2-neck flask under nitrogen atmosphere, intermediate (6) (2 g, 0.0032 mol), intermediate (3) (2 g, 0.006 mol), 2-propanol (0.13 mL, 0.003 mol), Pd(pph 3) ) 4 (0.03 g, 0.00003 mol) was added and 1,2-dimethoxyethane (50 mL) was added. The reaction was carried out by refluxing at 80° C. for 15 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with dichloromethane/distilled water to separate the organic layer. After all the solvent in the separated organic layer was blown off, the final material was obtained by purification by column chromatography.

1H NMR (CDCl3, 300 MHz); δ = 9.21 (d, -CH-), 9.0 (d, -CH-), 8.70 (d, -CH-), 8.42 (d, -CH-), 8.25 (s, -CH-), 7.18-7.55 (m, -CH-), 7.32 (d,-CH-), 7.05 (d,-CH-), 4.06 (t,-CH2-), 1.81 (t ,-CH-), 1.66 (m, -CH2-), 0.91 (d, -CH3-) 1 H NMR (CDCl 3 , 300 MHz); δ = 9.21 (d, -CH-), 9.0 (d, -CH-), 8.70 (d, -CH-), 8.42 (d, -CH-), 8.25 (s, -CH-), 7.18-7.55 (m, -CH-), 7.32 (d,-CH-), 7.05 (d,-CH-), 4.06 (t,-CH 2 -), 1.81 (t ,-CH-), 1.66 (m,- CH 2 -), 0.91 (d, -CH 3 -)

제조예 8: 화학식 8의 화합물의 제조Preparation Example 8: Preparation of the compound of Formula 8

Figure pat00078
Figure pat00078

중간체 (a)의 제조Preparation of intermediate (a)

질소 분위기 하에서 1,3-디브로모-5-헥실벤젠 (5 g, 0.0156 mol)을 탈수 디에틸 에테르 (20 mL)에 녹였다. 0 ℃에서 n-부틸 리튬 (10 mL, 0.017 mol)을 첨가한 후에 3시간 교반하였다. 2시간 후에 디클로로디페닐실란을 넣고 실온에서 12시간 정도 반응을 진행하였다. 증류수를 넣어 반응을 종료시킨 후, 디에틸 에테르로 추출하였다. 컬럼크로마토그래피(헥산)로 정제하여 중간체 (a)를 수득하였다.1,3-dibromo-5-hexylbenzene (5 g, 0.0156 mol) was dissolved in dehydrated diethyl ether (20 mL) under a nitrogen atmosphere. After adding n-butyl lithium (10 mL, 0.017 mol) at 0 °C, the mixture was stirred for 3 hours. After 2 hours, dichlorodiphenylsilane was added and the reaction was performed at room temperature for about 12 hours. After adding distilled water to complete the reaction, extraction was performed with diethyl ether. Purified by column chromatography (hexane) to obtain an intermediate (a).

중간체 (b)의 제조Preparation of intermediate (b)

질소 분위기 하에서 250 mL 2-목 플라스크에, 중간체 (a) (2 g, 0.003 mol), 6-브로모-3-피리디닐보론산 (1.22 g, 0.006 mol), Pd(pph3)4 (0.034 g, 0.00003 mol) 를 넣고, THF (70 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 70 mL)를 첨가하였다. 80 ℃ 에서 12시간동안 환류시켜 반응을 진행하였다.In a 250 mL 2-neck flask under nitrogen atmosphere, intermediate (a) (2 g, 0.003 mol), 6-bromo-3-pyridinylboronic acid (1.22 g, 0.006 mol), Pd(pph 3 ) 4 (0.034 g, 0.00003 mol) was added, and THF (70 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 70 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours.

반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피 (에틸 아세테이트:헥산 = 1:10 v/v) 로 정제하여 중간체 (b)를 수득하였다.After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvents in the separated organic layer were blown off, the mixture was purified by column chromatography (ethyl acetate:hexane = 1:10 v/v) to obtain an intermediate (b).

화학식 8의 화합물의 제조Preparation of the compound of formula 8

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.058 g, 0.02 mol)를 넣고 1시간동안 교반시켰다. 중간체 (b) (1 g, 0.0012 mol)을 넣고 DMSO (10 mL) 에 녹인 후, 천천히 적가하였다. 중간체 (b)를 모두 넣은 후 (4-하이드록시페닐)(페닐)메타논 (0.476 g, 0.0024 mol)을 DMSO (5 ml)에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피(에틸 아세테이트:헥산 = 1:20 v/v)로 정제하여 최종 물질인 화학식 8의 화합물을 수득하였다. In a nitrogen atmosphere, sodium hydride (0.058 g, 0.02 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. Intermediate (b) (1 g, 0.0012 mol) was added and dissolved in DMSO (10 mL), and then slowly added dropwise. After all the intermediate (b) was added, (4-hydroxyphenyl) (phenyl) methanol (0.476 g, 0.0024 mol) was dissolved in DMSO (5 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, work up was performed with ethyl acetate/distilled water. The mixture in the Crude state was purified by column chromatography (ethyl acetate:hexane = 1:20 v/v) to obtain the final material, the compound of Formula 8.

1H NMR (CDCl3, 300 MHz); δ = 7.97 (m, -CH-), 7.78 (d, -CH-), 7.64-7.37 (m, -CH-), 7.05 (d, -CH-), 6.60 (d, -CH-), 2.62 (t, -CH2-)　, 1.59 (m, -CH2-), 1.31(m, -CH2-), 0.88 (m, -CH3 ) 1 H NMR (CDCl 3 , 300 MHz); δ = 7.97 (m, -CH-), 7.78 (d, -CH-), 7.64-7.37 (m, -CH-), 7.05 (d, -CH-), 6.60 (d, -CH-), 2.62 (t, -CH 2 -), 1.59 (m, -CH 2 -), 1.31 (m, -CH 2 -), 0.88 (m, -CH 3 )

제조예 9: 화학식 9의 화합물의 제조Preparation Example 9: Preparation of the compound of formula 9

Figure pat00079
Figure pat00079

중간체 (1)의 제조Preparation of intermediate (1)

질소 분위기 하에서 500 mL 둥근 바닥 플라스크에 리튬금속 (0.455 g, 6.55 mol)을 넣어 준비하고, 반응 온도를 -15 ℃로 유지하였다. 디페닐아세틸렌(17.8 g, 0.1 mol)을 무수 에틸 에테르(90 mL)에 녹여, 플라스크에 천천히 적가하였다. 현탁액을 3.5시간 동안 상온에서 교반하였다. 남아있는 리튬 조각을 제거하였다. 반응 혼합물을 추가로 15시간 상온에서 교반하였다. 황색 침전물을 여과하여 에테르로 세척하였다. 진공오븐에서 건조하여 중간체 (1)를 수득하였다.Lithium metal (0.455 g, 6.55 mol) was added to a 500 mL round bottom flask under a nitrogen atmosphere to prepare, and the reaction temperature was maintained at -15 °C. Diphenylacetylene (17.8 g, 0.1 mol) was dissolved in anhydrous ethyl ether (90 mL) and slowly added dropwise to the flask. The suspension was stirred at room temperature for 3.5 hours. The remaining pieces of lithium were removed. The reaction mixture was further stirred at room temperature for 15 hours. The yellow precipitate was filtered and washed with ether. The intermediate (1) was obtained by drying in a vacuum oven.

중간체 (2)의 제조Preparation of intermediate (2)

질소 분위기 하에서 500 mL 둥근 바닥 플라스크에 중간체 (1) (3 g, 0.008 mol)을 넣고, THF (50 mL)를 넣었다. 디클로로(디메틸)실란 (1.1 g, 0.008 mol)을 첨가 하였다. 80 ℃에서 5시간동안 반응을 진행하였다. 반응 종료 후, 혼합물을 냉각시키고 여과하였다. 여액을 증류수와 에틸 아세테이트로 work up하여 유기물을 분리하였다. 컬럼크로마토 그래피로 중간체 (2)를 수득하였다.In a 500 mL round-bottom flask under a nitrogen atmosphere, intermediate (1) (3 g, 0.008 mol) was added, and THF (50 mL) was added. Dichloro(dimethyl)silane (1.1 g, 0.008 mol) was added. The reaction was carried out at 80° C. for 5 hours. After completion of the reaction, the mixture was cooled and filtered. The filtrate was worked up with distilled water and ethyl acetate to separate organic matter. Intermediate (2) was obtained by column chromatography.

중간체 (3)의 제조Preparation of intermediate (3)

질소 분위기 하에서 250 mL 둥근 바닥 플라스크에 NBS (3 g, 0.016 mol), AuCl3(0.048 g, 0.00016 mol) 을 넣었다. 중간체 (2) (6.6 g, 0.02 mol)를 넣고, 1,2-디클로로에탄 (80 mL)을 넣었다. 80 ℃ 에서 11시간동안 반응을 진행하였다. NBS (3 g, 0.016 mol) and AuCl 3 (0.048 g, 0.00016 mol) were added to a 250 mL round bottom flask under a nitrogen atmosphere. Intermediate (2) (6.6 g, 0.02 mol) was added, followed by 1,2-dichloroethane (80 mL). The reaction was performed at 80° C. for 11 hours.

반응 종료 후, 컬럼크로마토그래피로 중간체 (3)를 수득하였다.After completion of the reaction, intermediate (3) was obtained by column chromatography.

중간체 (4)의 제조Preparation of intermediate (4)

질소 분위기 하에서 250 mL 2-목 플라스크에, (4-하이드록시페닐)(페닐)메타논 (5 g, 0.025 mol), 3-브로모프로판-1-올 (3.5 mL, 0.025 mol), 포타슘 포스페이트 (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol)를 넣고 DSMO (100 mL)를 넣었다.In a 250 mL 2-neck flask under a nitrogen atmosphere, (4-hydroxyphenyl)(phenyl)methanone (5 g, 0.025 mol), 3-bromopropan-1-ol (3.5 mL, 0.025 mol), potassium phosphate (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol) was added and DSMO (100 mL) was added.

110 ℃에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 제거한 후, 컬럼크로마토그래피로 정제하여 중간체 (2)를 수득하였다.The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After removing all of the solvent in the separated organic layer, the intermediate (2) was obtained by column chromatography.

화학식 9의 화합물의 제조Preparation of the compound of formula 9

질소 분위기 하에서 250 mL 2-목 플라스크에, 중간체 (3) (2 g, 0.0035 mol), 중간체 (4) (1.8 g, 0.007 mol), 2-프로판올 (0.2 mL, 0.0035 mol), Pd(pph3)4 (0.03 g, 0.00003 mol) 를 넣고 1,2-디메톡시에탄 (30 mL)를 넣었다. 80 ℃ 에서 15시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 디클로로메탄/증류수로 추출하여 유기층을 분리하였다.In a 250 mL 2-neck flask under nitrogen atmosphere, intermediate (3) (2 g, 0.0035 mol), intermediate (4) (1.8 g, 0.007 mol), 2-propanol (0.2 mL, 0.0035 mol), Pd (pph 3) ) 4 (0.03 g, 0.00003 mol) was added and 1,2-dimethoxyethane (30 mL) was added. The reaction was carried out by refluxing at 80° C. for 15 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with dichloromethane/distilled water to separate the organic layer.

분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 최종물질 을 수득하였다.After all the solvents in the separated organic layer were blown off, the mixture was purified by column chromatography to obtain a final material.

1H NMR (CDCl3, 300 MHz); δ = 7.78 (m, -CH-), 7.64-7.30 (m, -CH-), 7.09 (d, -CH-), 6.99 (d, -CH-), 4.29 (t, -CH2-), 2.25 (m, -CH2-)　 1 H NMR (CDCl 3 , 300 MHz); δ = 7.78 (m, -CH-), 7.64-7.30 (m, -CH-), 7.09 (d, -CH-), 6.99 (d, -CH-), 4.29 (t, -CH 2 -), 2.25 (m, -CH 2 -)

제조예 10: 화학식 10의 화합물의 제조Preparation Example 10: Preparation of the compound of Formula 10

Figure pat00080
Figure pat00080

중간체 (1)의 제조Preparation of intermediate (1)

질소 분위기 하에서 250 mL 1-목 플라스크에, 1-(4-브로모페닐)2-페닐벤즈이미다졸(5 g, 0.014 mol), 비스(피나콜레이토)디보론 (3.6 g, 0.014 mol), 포타슘 아세테이트 (4.1 g, 0.042 mol), Pd(pph3)4 (0.8 g, 0.0007 mol)을 넣고 1,4-디옥산 (100 mL)를 넣어 교반시켰다. 110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 상온에서 식혀 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 감압제거한 후, 컬럼 크로마토그래피로 중간체 (1)를 수득하였다.In a 250 mL 1-neck flask under a nitrogen atmosphere, 1-(4-bromophenyl)2-phenylbenzimidazole (5 g, 0.014 mol), bis(pinacollato)diboron (3.6 g, 0.014 mol), Potassium acetate (4.1 g, 0.042 mol), Pd(pph 3 ) 4 (0.8 g, 0.0007 mol) was added and 1,4-dioxane (100 mL) was added and stirred. The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After removing the solvent of the separated organic layer under reduced pressure, intermediate (1) was obtained by column chromatography.

중간체 (2)의 제조Preparation of intermediate (2)

질소 분위기 하에서 200 mL 2-목 플라스크에, 중간체 (1) (4.3 g, 0.011 mol), 9,10-디브로모안트라센 (3.7 g, 0.011 mol), Pd(pph3)4 (0.6 g, 0.0005 mol)를 넣고, THF (100 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 100 mL)를 넣었다. 80 ℃ 에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제 하여 중간체 (2)를 수득하였다.In a 200 mL 2-neck flask under nitrogen atmosphere, intermediate (1) (4.3 g, 0.011 mol), 9,10-dibromoanthracene (3.7 g, 0.011 mol), Pd(pph 3 ) 4 (0.6 g, 0.0005) mol) was added, and THF (100 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 100 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvents in the separated organic layer were blown off, the intermediate was purified by column chromatography to obtain an intermediate (2).

중간체 (3)의 제조Preparation of intermediate (3)

질소 분위기 하에서 250 mL 1-목 플라스크에, 정제한 중간체 (2) (5 g, 0.0095 mol), 비스(피나콜레이토)디보론 (2.4 g, 0.0095 mol), 포타슘 아세테이트 (2.7 g, 0.028 mol), Pd(pph3)4 (0.5 g, 0.00048 mol)을 넣고 1,4-디옥산 (100 mL)를 넣어 교반시켰다. 110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후 상온에서 식혀 디클로로메탄/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 감압제거한 후, 컬럼 크로마토그래피로 중간체(3)를 수득하였다.In a 250 mL 1-neck flask under a nitrogen atmosphere, the purified intermediate (2) (5 g, 0.0095 mol), bis (pinacollato) diboron (2.4 g, 0.0095 mol), potassium acetate (2.7 g, 0.028 mol) , Pd(pph 3 ) 4 (0.5 g, 0.00048 mol) was added and 1,4-dioxane (100 mL) was added and stirred. The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with dichloromethane/distilled water to separate the organic layer. After removing the solvent of the separated organic layer under reduced pressure, the intermediate (3) was obtained by column chromatography.

중간체 (4)의 제조Preparation of intermediate (4)

질소 분위기 하에서 500 mL 2-목 플라스크에, 중간체 (3) (4 g, 0.0052 mol), 1,3,5-트리브로모벤젠 (1.6 g, 0.0052 mol), Pd(pph3)4 (0.4 g, 0.00026 mol)를 넣고, THF (80 mL)를 넣어 교반시켰다. 플라스크 안에 물질이 모두 녹으면 포타슘 카보네이트 용액 (2N, 80 mL)를 넣었다. 80 ℃에서 12시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 디클로로메탄/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피 로 정제하여 중간체 (4)를 수득하였다.In a 500 mL 2-neck flask under nitrogen atmosphere, intermediate (3) (4 g, 0.0052 mol), 1,3,5-tribromobenzene (1.6 g, 0.0052 mol), Pd(pph 3 ) 4 (0.4 g , 0.00026 mol) was added, and THF (80 mL) was added and stirred. When all the substances were dissolved in the flask, potassium carbonate solution (2N, 80 mL) was added. The reaction was carried out by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with dichloromethane/distilled water to separate the organic layer. After all the solvent in the separated organic layer was blown off, the intermediate was purified by column chromatography to obtain an intermediate (4).

중간체 (5)의 제조Preparation of intermediate (5)

질소 분위기 하에서 250 mL 2-목 플라스크에, (4-하이드록시페닐)(페닐)메타논 (5 g, 0.025 mol), 3-브로모프로판-1-올 (3.5 mL, 0.025 mol), 포타슘 포스페이트 (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol)를 넣고 DSMO (100 mL)를 넣었다.In a 250 mL 2-neck flask under a nitrogen atmosphere, (4-hydroxyphenyl)(phenyl)methanone (5 g, 0.025 mol), 3-bromopropan-1-ol (3.5 mL, 0.025 mol), potassium phosphate (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol) was added and DSMO (100 mL) was added.

110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 중간체 (2)를 수득하였다.The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvents in the separated organic layer were blown away, the intermediate was purified by column chromatography to obtain an intermediate (2).

화학식 10의 화합물의 제조Preparation of the compound of formula 10

질소 분위기 하에서 250 mL 2-목 플라스크에, (4-하이드록시페닐)(페닐)메타논 (5 g, 0.025 mol), 3-브로모프로판-1-올 (3.5 mL, 0.025 mol), 포타슘 포스페이트 (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol)를 넣고 DSMO (100 mL)를 넣는다.In a 250 mL 2-neck flask under a nitrogen atmosphere, (4-hydroxyphenyl)(phenyl)methanone (5 g, 0.025 mol), 3-bromopropan-1-ol (3.5 mL, 0.025 mol), potassium phosphate Add (13.2 g, 0.0625 mol), CuI (0.47 g, 0.0025 mol) and DSMO (100 mL).

110 ℃ 에서 24시간동안 환류시켜 반응을 진행하였다. 반응 종료 후, 상온에서 식히고 에틸 아세테이트/증류수로 추출하여 유기층을 분리하였다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피로 정제하여 중간체 (2)를 수득하였다.The reaction was carried out by refluxing at 110° C. for 24 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with ethyl acetate/distilled water to separate the organic layer. After all the solvents in the separated organic layer were blown away, the intermediate was purified by column chromatography to obtain an intermediate (2).

제조예 11: 화학식 11의 화합물의 제조Preparation Example 11: Preparation of the compound of Formula 11

Figure pat00081
Figure pat00081

중간체 (a)의 제조Preparation of intermediate (a)

2-목 둥근바닥 플라스크에 4-브로모벤조일 클로라이드 (6.75 g, 0.03 mol)와 트리에틸아민 (2.75 g, 0.03 mol), 클로로포름 (30 ml)을 넣고 교반하였다. 0 ℃ 로 맞춘 뒤 하이드라진 모노하이드레이트 (0.75 g, 0.15 mol)를 천천히 적가하였다.In a 2-neck round bottom flask, 4-bromobenzoyl chloride (6.75 g, 0.03 mol), triethylamine (2.75 g, 0.03 mol), and chloroform (30 ml) were added and stirred. After adjusting to 0 ℃, hydrazine monohydrate (0.75 g, 0.15 mol) was slowly added dropwise.

반응물을 실온(RT)에서 약 4시간정도 교반하여 반응을 진행하였다. 반응물의 용매를 날려준 뒤 PE/Water 로 약 2회 세척하였다. 증발기(Evaporator)로 건조 시켜 중간체 (a)를 수득하였다.The reaction was stirred at room temperature (RT) for about 4 hours to proceed with the reaction. After blowing off the solvent of the reactant, it was washed about twice with PE/Water. The intermediate (a) was obtained by drying with an evaporator.

중간체 (b)의 제조Preparation of intermediate (b)

2-목 둥근바닥 플라스크에 4-헥실아닐린 (8.95 g, 0.06 mol)과 1,2-디클로로벤젠 (10 ml)을 첨가하였다. PCl3 (2.06 g, 0.15 mol)를 첨가하였다. 반응물을 100 ℃ 에서 약 1h 정도 교반하였다. 중간체 (a) (5.3 g, 0.01 mol)를 반응 둥근바닥 플라스크에 넣고 약 200 ℃ 에서 24 시간동안 반응을 진행하였다. 반응물을 실온(RT)으로 식혀준 뒤 2N HCl (100ml)를 첨가하였다. 반응물을 Celite로 필터 링하였다. 디클로로메탄/물로 work up 한 뒤, MgSO4 로 물기를 제거하였다. 증류에 의해, 잔류 1,2-디클로로벤젠을 제거하였다. Crude solid를 컬럼 (에틸 아세테이트:디클로로메탄 = 1:9 v/v)을 통해 정제하여 중간체 (b)를 수득하였다.To a two-neck round bottom flask, 4-hexylaniline (8.95 g, 0.06 mol) and 1,2-dichlorobenzene (10 ml) were added. PCl 3 (2.06 g, 0.15 mol) was added. The reaction was stirred at 100° C. for about 1 h. Intermediate (a) (5.3 g, 0.01 mol) was added to the reaction round bottom flask and about 200 The reaction was carried out at °C for 24 hours. After cooling the reaction to room temperature (RT), 2N HCl (100ml) was added. The reaction was filtered with Celite. After work up with dichloromethane/water, water was removed with MgSO 4. Residual 1,2-dichlorobenzene was removed by distillation. Crude solid was purified through a column (ethyl acetate:dichloromethane = 1:9 v/v) to obtain an intermediate (b).

화학식 11의 화합물의 제조Preparation of the compound of formula 11

질소분위기 하에서 100 mL 2목 플라스크에 소듐 하이드라이드 (0.048 g, 0.002 mol)를 넣고 1시간동안 교반시켰다. (4-하이드록시페닐)(페닐)메타논 (3 g, 0.015 mol)을 넣고 DMSO (10 mL) 에 녹인 후, 천천히 적가하였다. 물질을 모두 넣은 후 중간체 (b) (3.53 g, 0.0065 mol)를 DMSO (30 ml)에 녹여 첨가하였다. 80 ℃에서 24시간동안 반응을 진행시켰다. 반응 종료 후 에틸 아세테이트/증류수로 work up 하였다. Crude 상태의 혼합물을 컬럼크로마토그래피로 정제하여 최종물질을 수득하였다.In a nitrogen atmosphere, sodium hydride (0.048 g, 0.002 mol) was added to a 100 mL two-necked flask and stirred for 1 hour. (4-hydroxyphenyl)(phenyl)methanone (3 g, 0.015 mol) was added and dissolved in DMSO (10 mL), and then slowly added dropwise. After adding all the substances, intermediate (b) (3.53 g, 0.0065 mol) was dissolved in DMSO (30 ml) and added. The reaction was allowed to proceed at 80° C. for 24 hours. After completion of the reaction, work up was performed with ethyl acetate/distilled water. The crude mixture was purified by column chromatography to obtain a final material.

1H NMR (CDCl3, 300 MHz); δ = 8.04 (d, -CH-), 7.78-7.55 (m, -CH-), 7.29-7.24 (m, -CH-), 6.93 (d, -CH-), 2.62 (t, CH2-), 1.59 (t, -CH2-), 1.31-1.29 (s, -CH2- ), 0.88 (t, -CH3-)　 1 H NMR (CDCl 3 , 300 MHz); δ = 8.04 (d, -CH-), 7.78-7.55 (m, -CH-), 7.29-7.24 (m, -CH-), 6.93 (d, -CH-), 2.62 (t, CH 2 -) , 1.59 (t, -CH 2 -), 1.31-1.29 (s, -CH 2- ), 0.88 (t, -CH 3 -)

실시예 1:Example 1:

ITO 유리 기판을 아세톤, 순수물과 이소프로필 알코올 속에서 각 15분 동안 초음파 세정한 후, 15분 동안 UV 오존 세정하여 사용하였다. The ITO glass substrate was ultrasonically cleaned for 15 minutes each in acetone, pure water and isopropyl alcohol, followed by UV ozone cleaning for 15 minutes.

다음으로 PEDOT:PSS (Clevios P VP AI4083) 용액을 상기 층의 위에 20 nm의 두께로 스핀코팅하여 정공 주입층을 형성하였다.Next, a PEDOT:PSS (Clevios P VP AI4083) solution was spin-coated on the layer to a thickness of 20 nm to form a hole injection layer.

다음으로 상기 층의 위에, 제조예 1에서 제조 화학식 1의 화합물을 10wt%의 클로로벤젠 용액을 만들어 20nm의 두께로 스핀코팅(3000rpm, 40초)한 후, 2 mW/cm2 의 254 nm 파장을 가지는 UV를 5분간 조사하여 클로로벤젠에 녹지 않는 정공 수송층을 형성하였다.Next, on the layer, a 10 wt% chlorobenzene solution of the compound of Formula 1 prepared in Preparation Example 1 was prepared and spin-coated (3000 rpm, 40 seconds) to a thickness of 20 nm, and then a wavelength of 254 nm of 2 mW/cm 2 was applied. Branches were irradiated with UV for 5 minutes to form a hole transport layer insoluble in chlorobenzene.

이어서, 상기 정공 수송층 위에 host로써 제조예 3에서 제조된 화학식 3의 화합물과 8%의 Ir(mppy)3을 클로로벤젠에 녹여 40nm의 두께로 스핀코팅(2000rpm, 40초) 한 후 2 mW/cm2 의 254 nm 파장을 가지는 UV를 5분간 조사하여 클로로벤젠에 녹지 않는 발광층을 형성하였다.Subsequently, as a host on the hole transport layer, the compound of Formula 3 and 8% of Ir(mppy) 3 prepared in Preparation Example 3 were dissolved in chlorobenzene and spin-coated to a thickness of 40 nm (2000 rpm, 40 seconds), and then 2 mW/cm 2 was irradiated with UV having a wavelength of 254 nm for 5 minutes to form a light emitting layer insoluble in chlorobenzene.

이어서, 발광층 위에 전자수송층으로, 제조예 7에서 제조된 화학식 7의 화합물을 10wt%의 클로로벤젠 용액을 만들어 20nm의 두께로 스핀코팅(3000rpm, 40초)한 후, 2 mW/cm2 의 254 nm파장을 가지는 UV를 5분간 조사하여 클로로벤젠에 녹지 않는 전자수송층을 형성하였다.Subsequently, as an electron transport layer on the emission layer, a 10 wt% chlorobenzene solution was prepared with the compound of Formula 7 prepared in Preparation Example 7 and spin-coated to a thickness of 20 nm (3000 rpm, 40 seconds), and then 2 mW/cm 2 of 254 nm UV having a wavelength was irradiated for 5 minutes to form an electron transport layer insoluble in chlorobenzene.

이 후, 상기 전자수송층 상부에 LiF 10Å(전자 주입층)과 Al 1000Å(음극)을 순차적으로 진공 증착하여, 유기전자소자(구체적으로는 유기발광소자)를 제조하였다.Thereafter, 10 Å of LiF (electron injection layer) and 1000 Å of Al (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic electronic device (specifically, an organic light emitting device).

실시예 2:Example 2:

ITO 유리 기판을 아세톤, 순수물과 이소프로필 알코올 속에서 각 15분 동안 초음파 세정한 후, 15분 동안 UV 오존 세정하여 사용하였다. The ITO glass substrate was ultrasonically cleaned for 15 minutes each in acetone, pure water and isopropyl alcohol, followed by UV ozone cleaning for 15 minutes.

다음으로 PEDOT:PSS (Clevios P VP AI4083)용액을 상기 층의 위에 20nm의 두께로 스핀코팅하여 정공 주입층을 형성하였다.Next, a PEDOT:PSS (Clevios P VP AI4083) solution was spin-coated on the layer to a thickness of 20 nm to form a hole injection layer.

다음으로 상기 층의 위에, 제조예 6에서 제조된 화학식 6의 화합물을 5wt%의 클로로벤젠 용액을 만들어 20nm의 두께로 스핀코팅(3000rpm, 40초)한 후, 2 mW/cm2 의 254 nm파장을 가지는 UV를 5분간 조사하여 클로로벤젠에 녹지 않는 정공 수송층을 형성하였다.Next, on the layer, the compound of Formula 6 prepared in Preparation Example 6 was spin-coated to a thickness of 20 nm by making a 5 wt% chlorobenzene solution (3000 rpm, 40 seconds), followed by a 254 nm wavelength of 2 mW/cm 2 A hole transport layer insoluble in chlorobenzene was formed by irradiation with UV for 5 minutes.

이어서, 상기 정공 수송층 위에 host로써 제조예 2에서 제조된 화학식 2의 화합물과 8%의 Ir(mppy)3을 클로로벤젠에 녹여 40nm의 두께로 스핀코팅(2000rpm, 40초) 한 후 2 mW/cm2 의 254 nm 파장을 가지는 UV를 5분간 조사하여 클로로벤젠에 녹지 않는 발광층을 형성하였다.Subsequently, as a host on the hole transport layer, the compound of Formula 2 and 8% of Ir(mppy) 3 prepared in Preparation Example 2 were dissolved in chlorobenzene and spin-coated to a thickness of 40 nm (2000 rpm, 40 seconds), and then 2 mW/cm 2 was irradiated with UV having a wavelength of 254 nm for 5 minutes to form a light emitting layer insoluble in chlorobenzene.

이어서, 발광층 위에 전자수송층으로, 제조예 10에서 제조된 화학식 10의 화합물을 10wt%의 클로로벤젠 용액으로 만들어 20nm의 두께로 스핀코팅(3000rpm, 40초)한 후, 2 mW/cm2 의 254 nm파장을 가지는 UV를 5분간 조사하여 클로로벤젠에 녹지 않는 전자수송층을 형성하였다.Subsequently, as an electron transport layer on the emission layer, the compound of Formula 10 prepared in Preparation Example 10 was made into a 10 wt% chlorobenzene solution and spin-coated to a thickness of 20 nm (3000 rpm, 40 seconds), and then 2 mW/cm 2 of 254 nm UV having a wavelength was irradiated for 5 minutes to form an electron transport layer insoluble in chlorobenzene.

이 후, 상기 전자수송층 상부에 LiF 10Å(전자 주입층)과 Al 1000Å(음극)을 순차적으로 진공 증착하여, 유기전자소자(구체적으로는 유기발광소자)를 제조하였다.Thereafter, 10 Å of LiF (electron injection layer) and 1000 Å of Al (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic electronic device (specifically, an organic light emitting device).

비교예 1:Comparative Example 1:

ITO 유리 기판을 아세톤, 순수물과 이소프로필 알코올 속에서 각 15분 동안 초음파 세정한 후, 15분 동안 UV 오존 세정하여 사용하였다. The ITO glass substrate was ultrasonically cleaned for 15 minutes each in acetone, pure water and isopropyl alcohol, followed by UV ozone cleaning for 15 minutes.

다음으로 PEDOT:PSS (Clevios P VP AI4083)용액을 상기 층의 위에 20nm의 두께로 스핀코팅하여 정공 주입층을 형성하였다.Next, a PEDOT:PSS (Clevios P VP AI4083) solution was spin-coated on the layer to a thickness of 20 nm to form a hole injection layer.

다음으로 상기 층의 위에 VNPB (N4,N4′'-디(나프탈렌-1-일)-N4,N4′'-비스(4-비닐페닐)바이페닐-4,4′'-디아민)을 10wt%의 클로로벤젠 용액으로 만들어 20nm의 두께로 스핀코팅(3000rpm, 40초)한 후, 질소 분위기에서 180℃로 1시간동안 열처리를 하여 클로로벤젠에 녹지 않는 정공 수송층을 형성하였다.Next, 10 wt% of VNPB (N4,N4′′-di(naphthalen-1-yl)-N4,N4′′-bis(4-vinylphenyl)biphenyl-4,4′′-diamine) on the layer After making a chlorobenzene solution of 20 nm and spin coating (3000 rpm, 40 seconds) to a thickness of 20 nm, heat treatment was performed at 180° C. for 1 hour in a nitrogen atmosphere to form a hole transport layer insoluble in chlorobenzene.

이어서, 상기 정공 수송층 위에 host로써 DV-CBP (4,4'-비스(3-((4-비닐페녹시)메틸)-9H-카바졸-9-일)비페닐)과 8%의 Ir(mppy)3을 클로로벤젠에 녹여 40nm의 두께로 스핀코팅(2000rpm, 40초) 한 후, 질소 분위기에서 180℃에서 1시간 동안 열처리를 하여 클로로벤젠에 녹지 않는 발광층을 형성하였다.Then, DV-CBP (4,4'-bis(3-((4-vinylphenoxy)methyl)-9H-carbazol-9-yl)biphenyl) and 8% Ir( mppy) 3 was dissolved in chlorobenzene, spin-coated to a thickness of 40 nm (2000 rpm, 40 seconds), and then heat-treated at 180° C. for 1 hour in a nitrogen atmosphere to form a light emitting layer insoluble in chlorobenzene.

이어서, 발광층 위에 전자수송층으로 TPBi 증착하여 전자수송층을 형성하고, 상기 전자수송층 상부에 LiF 10Å(전자 주입층)과 Al 1000Å(음극)을 순차적으로 진공 증착하여, 유기전자소자(구체적으로는 유기발광소자)를 제조하였다.Subsequently, TPBi is deposited as an electron transport layer on the emission layer to form an electron transport layer, and LiF 10Å (electron injection layer) and Al 1000Å (cathode) are sequentially vacuum-deposited on the electron transport layer, and an organic electronic device (specifically, organic light emission). Device) was prepared.

평가예 1: 구동전압Evaluation Example 1: Driving voltage

상기 실시예 1, 실시예 2 및 비교예 각각에서 제조된 유기전자소자에 대하여, 전압-전류계(Keithley 2400) 를 이용하여 luminance 100cd/m2에서 구동전압을 측정하고, 그 결과를 하기 표 4에 기재하였다.For the organic electronic devices prepared in each of Examples 1, 2, and Comparative Examples, a voltage-ammeter (Keithley 2400) was used to measure the driving voltage at luminance 100 cd/m2, and the results are shown in Table 4 below. I did.

평가예: 발광 효율Evaluation example: luminous efficiency

발광효율은 PR-650 SpectraScan Spectrophotometer를 이용하여 효율의 최대치를 측정하였다.The maximum luminous efficiency was measured using a PR-650 SpectraScan Spectrophotometer.

평가예 3: 전력효율Evaluation Example 3: Power efficiency

제조된 유기전자소자에 대해, 전압을 0V 부터 10V까지 상승시키면서 전류-전압계(Keithley 2400)를 이용하여 단위소자에 흐르는 전류값을 측정하고, 측정된 전류값을 면적으로 나누어 전류밀도를 수득하였다. 이와 같이 수득된 전류밀도 값과, 전술한 휘도 및 전압을 이용하여 최대치 전력 효율을 측정하여 그 결과를 하기 표 1에 기재하였다.For the prepared organic electronic device, while increasing the voltage from 0V to 10V, a current-voltmeter (Keithley 2400) was used to measure the current value flowing through the unit device, and the measured current value was divided by the area to obtain a current density. The maximum power efficiency was measured using the current density value obtained as described above and the luminance and voltage described above, and the results are shown in Table 1 below.

평가예 4: 휘도Evaluation Example 4: Brightness

상기 실시예 1, 실시예 2 및 비교예 각각에서 제조된 유기전자소자에 대하여 전압을 0 V부터 15 V까지 상승시키면서 휘도계 (PR-650 SpectraScan Spectrophotometer) 를 이용하여 휘도를 측정하고, 그 결과를 하기 표 1에 기재하였다.The luminance was measured using a luminance meter (PR-650 SpectraScan Spectrophotometer) while increasing the voltage from 0 V to 15 V for the organic electronic device prepared in each of Examples 1, 2 and Comparative Examples, and the result was measured. It is shown in Table 1 below.

Figure pat00082
Figure pat00082

본 발명의 화합물을 호스트로 도입하는 전력 효율이 크게 증가하는 것을 확인할 수 있다. 이러한 결과는 전자 주입 및 전자 수송 능력이 우수한 본 발명의 제3화합물을 호스트로 추가하여 도펀트와 호스트 간 LUMO 에너지 레벨 차이로 인한 트랩 현상을 최소화함으로써 얻을 수 있는 것이다.It can be seen that the power efficiency of introducing the compound of the present invention into the host is greatly increased. This result can be obtained by minimizing the trap phenomenon due to the difference in LUMO energy level between the dopant and the host by adding the third compound of the present invention, which has excellent electron injection and electron transport capabilities, as a host.

본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains, other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that it can be implemented with Therefore, it should be understood that the embodiments described above are illustrative and non-limiting in all respects.

Claims (6)

하기 화학식 I 또는 화학식 II로 표시되는 벤조페논 작용기 함유 화합물:
[화학식 I]
Ar-(R1-R2-Bp)m
상기 화학식에서,
m은 1 내지 10 이고,
Ar은 하기로 표시되는 것 중 하나이고,
Figure pat00083
,
Figure pat00084
,
Figure pat00085
,
R1 및 R2는 각각 독립적으로, 단순 결합, -O-, 치환 또는 비치환된 C6-C30아릴렌기, 치환 또는 비치환된 C3-C30 헤테로아릴렌기, 치환 또는 비치환된 C1-C10 알킬렌기이고,
Bp은 벤조페논 작용기로부터 유래된 1가 연결기이다.
[화학식 II]
Figure pat00086

상기 화학식에서,
n은 1 이상이고,
Ar'은 하기로 표시되는 것 중 하나이고,
Figure pat00087
,
Figure pat00088
,
Figure pat00089
,
R3 및 R4는 각각 독립적으로, 단순 결합, -O-, 치환 또는 비치환된 C6-C30아릴렌기, 치환 또는 비치환된 C3-C30 헤테로아릴렌기, 치환 또는 비치환된 C6-C30 융합된 아릴렌기, 치환 또는 비치환된 C1-C10 알킬렌기이고,
Bp'은 벤조페논 작용기로부터 유래된 1가 연결기이다.A compound containing a benzophenone functional group represented by the following formula (I) or formula (II):
[Formula I]
Ar-(R 1 -R 2 -Bp) m
In the above formula,
m is 1 to 10,
Ar is one of those represented by the following,
Figure pat00083
,
Figure pat00084
,
Figure pat00085
,
R 1 and R 2 are each independently a simple bond, -O-, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 1 -C 10 alkylene group,
Bp is a monovalent linking group derived from a benzophenone functional group.
[Formula II]
Figure pat00086

In the above formula,
n is 1 or more,
Ar' is one of those represented by the following,
Figure pat00087
,
Figure pat00088
,
Figure pat00089
,
R 3 and R 4 are each independently a simple bond, -O-, a substituted or unsubstituted C 6 -C 30 arylene group, a substituted or unsubstituted C 3 -C 30 heteroarylene group, a substituted or unsubstituted C 6 -C 30 fused arylene group, substituted or unsubstituted C 1 -C 10 alkylene group,
Bp' is a monovalent linking group derived from a benzophenone functional group. 제1항에 있어서,
상기 벤조페논 작용기를 포함하는 화합물이 하기 화학식 1, 2, 및 6으로부터 선택된 1종 또는 2종 이상의 화합물인 벤조페논 작용기 함유 화합물:
[화학식 1]
Figure pat00090

[화학식 2]
Figure pat00091

[화학식 6]
Figure pat00092

(상기에서 n은 1 이상이다).The method of claim 1,
The compound containing the benzophenone functional group is one or two or more compounds selected from Formulas 1, 2, and 6 below:
[Formula 1]
Figure pat00090

[Formula 2]
Figure pat00091

[Formula 6]
Figure pat00092

(In the above, n is 1 or more). 제1항의 벤조페논 작용기 함유 화합물을 포함하는 광경화 조성물.A photocurable composition comprising the benzophenone functional group-containing compound of claim 1. 제1전극; 제2전극; 및 상기 제1전극과 상기 제2전극 사이에 제1항의 벤조페논 작용기 함유 화합물의 광경화물을 포함한 유기물층을 구비한 유기전자소자.A first electrode; A second electrode; And an organic material layer including a photocured product of the compound containing the benzophenone functional group of claim 1 between the first electrode and the second electrode. 제4항에 있어서,
상기 유기물층이 정공수송층이고,
상기 정공수송층이 하기 화학식 1, 2, 및 6의 화합물 중 1종 이상의 벤조페논 작용기 함유 화합물의 광경화물을 포함하는 유기전자소자:
[화학식 1]
Figure pat00093

[화학식 2]
Figure pat00094

[화학식 6]
Figure pat00095

(상기에서 n은 1 이상이다)The method of claim 4,
The organic material layer is a hole transport layer,
An organic electronic device in which the hole transport layer comprises a photocured product of at least one benzophenone functional group-containing compound among the compounds of Formulas 1, 2, and 6:
[Formula 1]
Figure pat00093

[Formula 2]
Figure pat00094

[Formula 6]
Figure pat00095

(In the above, n is 1 or more) 제 1 기판과;
상기 제 1 기판에 위치하는 구동 박막트랜지스터와;
상기 제 1 기판에 위치하며 상기 구동 박막트랜지스터에 연결되는 발광다이오드로서, 제1항의 벤조페논 작용기 함유 화합물의 광경화물을 적어도 하나의 유기물층에 포함하는 유기전자소자와;
상기 유기전자소자를 덮고 상기 제 1 기판과 합착되는 제 2 기판을 포함하는 표시 장치.A first substrate;
A driving thin film transistor positioned on the first substrate;
An organic electronic device disposed on the first substrate and connected to the driving thin film transistor, comprising a photocured product of the benzophenone functional group-containing compound of claim 1 in at least one organic material layer;
A display device including a second substrate covering the organic electronic device and bonded to the first substrate.
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